Composition for forming silicon-containing resist underlayer film and patterning process

ABSTRACT

A composition for forming a silicon-containing resist underlayer film includes: a thermosetting silicon-containing material containing any one or more of a partial structure shown by the general formula (Sx-1), (Sx-2), and (Sx-3); and a compound shown by the general formula (P-0), where R1 represents an organic group that has or generates a silanol group, a hydroxy group, or a carboxy group; R2 and R3 are each independently the same as R1 or each represent a hydrogen atom or a monovalent substituent having 1 to 30 carbon atoms; R100 represents a divalent organic group substituted with a fluorine atom; R101 and R102 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R103 represents a divalent hydrocarbon group having 1 to 20 carbon atoms; and L104 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a Division of application Ser. No. 16/928,777 filed Jul. 14,2020, which claims priority to JP 2019-135144 filed Jul. 23, 2019. Thedisclosure of the prior applications is hereby incorporated by referenceherein in its entirety.

TECHNICAL FIELD

The present invention relates to a composition for forming asilicon-containing resist underlayer film and a patterning process usingthe composition.

BACKGROUND ART

As Large-Scale Integrated circuits (LSIs) advance toward higherintegration and higher processing speed, miniaturization in pattern rulehas been required. In this situation, various technologies have beendeveloped in regard to how patterning process can be performed morefinely and precisely with light sources used in photolithography using achemically amplified resist, which is a commonly-employed technique atpresent.

Meanwhile, as the miniaturization advances, light diffraction phenomenonis approaching the physical limit. Consequently, the contrast ofexposure light employed in patterning has been lowered. Such physicallimit causes low dissolution contrast in positive resist films, andthereby degrades focus margin and resolution of hole patterns and trenchpatterns. To prevent the degradation of patterning performance in such alimiting state, a technique is required which enhances the dissolutioncontrast of resist films. As a method for enhancing the dissolutioncontrast of a chemically amplified resist, efforts have been made byutilizing the proliferation mechanism of an acid generated from aphoto-acid generator so as to increase sensitivity and minimize theinfluence from the lowered contrast of exposure light.

Under such circumstances, organic solvent development is attractingattention as a technique for fine patterning. For example, forresolution of extremely fine hole patterns that cannot be achieved witha positive tone by negative tone exposure, it is possible to formnegative patterns by organic solvent development using a high-resolutionpositive resist composition. Furthermore, a study is being made onobtaining twice as much resolving power by combining two developments:alkaline development and organic solvent development. As an ArF resistcomposition for negative tone development with an organic solvent, aconventional positive-type ArF resist composition can be used, and forexample, patterning processes are shown in Patent Documents 1 to 3.

CITATION LIST Patent Literature

-   Patent Document 1: Japanese Unexamined Patent Application    Publication No. 2008-281974-   Patent Document 2: Japanese Unexamined Patent Application    Publication No. 2008-281980-   Patent Document 3: Japanese Unexamined Patent Application    Publication No. 2009-53657

SUMMARY OF INVENTION Technical Problem

The present inventors have hitherto presented, for example, JP2012-194216 A, JP 2012-237975 A, JP 2013-33187 A, JP 2013-41140 A, JP2013-114059 A, JP 2013-167669 A, JP 2013-166812 A, and JP 2013-224279 Athat disclose silicon-containing resist underlayer films suitable fornegative tone patterning by developing a positive-type resist withorganic solvent. However, recently, a higher-precision edge roughness(LWR) and critical dimension uniformity (CDU) of hole patterns arerequired in patterning.

The present invention has been accomplished in view of theabove-described circumstances, and an object of the present invention isto provide a composition for forming a silicon-containing resistunderlayer film that can form resist patterns excellent in LWR and CDU,and a patterning process using this composition.

Solution to Problem

To solve the above-described problem, the present invention provides acomposition for forming a silicon-containing resist underlayer filmcomprising: a thermosetting silicon-containing material containing anyone or more of a repeating unit shown by the following general formula(Sx−1), a repeating unit shown by the following general formula (Sx−2),and a partial structure shown by the following general formula (Sx−3);and a compound shown by the following general formula (P−0),

wherein R¹ represents an organic group having one or more silanolgroups, hydroxy groups, or carboxy groups, or an organic group fromwhich a protecting group is eliminated by an action of acid and/or heatto generate one or more silanol groups, hydroxy groups, or carboxygroups; R² and R³ are each independently the same as R¹ or eachrepresent a hydrogen atom or a monovalent substituent having 1 to 30carbon atoms, and

wherein in the formula (P−0), R¹⁰⁰ represents a divalent organic groupsubstituted with one or more fluorine atoms, R¹⁰¹ and R¹⁰² eachindependently represents a linear, branched, or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms optionally substitutedwith a hetero atom or optionally interposed by a hetero atom; R¹⁰³represents a linear, branched, or cyclic divalent hydrocarbon grouphaving 1 to 20 carbon atoms optionally substituted with a hetero atom oroptionally interposed by a hetero atom; R¹⁰¹ and R¹⁰², or R¹⁰¹ and R¹⁰³,are optionally bonded to each other to form a ring with a sulfur atom inthe formula; and L¹⁰⁴ represents a single bond or a linear, branched, orcyclic divalent hydrocarbon group having 1 to 20 carbon atoms optionallysubstituted with a hetero atom or optionally interposed by a heteroatom.

A resist pattern excellent in LWR and CDU can be formed with such acomposition for forming a silicon-containing resist underlayer film.

The composition for forming a silicon-containing resist underlayer filmmay further comprise a crosslinking catalyst.

A silicon-containing resist underlayer film crosslinked at high densitycan be formed with such a composition for forming a silicon-containingresist underlayer film since the crosslinking catalyst can promotesiloxane bond formation when a thermosetting polysiloxane is cured.

In this case, the crosslinking catalyst may be a sulfonium salt, aniodonium salt, a phosphonium salt, an ammonium salt or a polysiloxanehaving a structure partially containing one of these salts, or analkaline metal salt.

A resist pattern more excellent in LWR and CDU can be formed bycombining such a crosslinking catalyst with the thermosettingsilicon-containing material of the present invention.

The composition for forming a silicon-containing resist underlayer filmmay further comprise a nitrogen-containing compound having anacid-decomposable substituent.

Such a composition for forming a silicon-containing resist underlayerfilm can inactivate excess acid by containing the nitrogen-containingcompound, and in this manner, diffusion of acid to the upper layerresist can be suppressed, and it is possible to form an upper layerresist pattern that is even more excellent in LWR and CDU.

Furthermore, the present invention provides a patterning processcomprising:

forming an organic underlayer film on a body to be processed using acoating-type organic underlayer film material;

forming a silicon-containing resist underlayer film on the organicunderlayer film using the composition for forming a silicon-containingresist underlayer film described above;

forming a photoresist film on the silicon-containing resist underlayerfilm using a chemically amplified resist composition;

exposing the photoresist film after a heat treatment and dissolving anunexposed portion of the photoresist film using an organic solventdeveloper to form a negative-type pattern;

transferring the pattern to the silicon-containing resist underlayerfilm by dry etching using the photoresist film having the formed patternas a mask;

transferring the pattern to the organic underlayer film by dry etchingusing the silicon-containing resist underlayer film having thetransferred pattern as a mask; and

transferring the pattern to the body to be processed by dry etchingusing the organic underlayer film having the transferred pattern as amask.

Using the inventive composition for forming a silicon-containing resistunderlayer film, an upper layer resist pattern with favorable LWR andCDU can be formed, and in addition, a semiconductor-device pattern canbe formed on a substrate with high yield since the silicon-containingresist underlayer film formed in this manner has excellent dry etchingselectivity relative to an upper layer resist (photoresist film) and anorganic underlayer film.

Furthermore, the present invention also provides a patterning processcomprising:

forming an organic hard mask mainly containing carbon on a body to beprocessed by a CVD method; forming a silicon-containing resistunderlayer film on the organic hard mask using the composition forforming a silicon-containing resist underlayer film described above;

forming a photoresist film on the silicon-containing resist underlayerfilm using a chemically amplified resist composition;

exposing the photoresist film after a heat treatment and dissolving anunexposed portion of the photoresist film using an organic solventdeveloper to form a negative-type pattern;

transferring the pattern to the silicon-containing resist underlayerfilm by dry etching using the photoresist film having the formed patternas a mask;

transferring the pattern to the organic hard mask by dry etching usingthe silicon-containing resist underlayer film having the transferredpattern as a mask; and

transferring the pattern to the body to be processed by dry etchingusing the organic hard mask having the transferred pattern as a mask.

Using the inventive composition for forming a silicon-containing resistunderlayer film, an upper layer resist pattern with favorable LWR andCDU can be formed, and in addition, a semiconductor-device pattern canbe formed on a substrate with high yield since the silicon-containingresist underlayer film formed in this manner has excellent dry etchingselectivity relative to an upper layer resist (photoresist film) and anorganic hard mask.

In the patterning process, the pattern may be formed in the photoresistfilm by a photolithography with a wavelength of 10 nm or more and 300 nmor less, direct drawing with an electron beam, nanoimprinting, or acombination thereof.

A suitable negative-type resist pattern can be obtained by performing atreatment in accordance with necessity after patterning under conditionsadapted to the photoresist film.

Furthermore, in the patterning process, the body to be processed may bea semiconductor device substrate, a metal film, an alloy film, a metalcarbide film, a metal oxide film, a metal nitride film, a metaloxycarbide film, or a metal oxynitride film.

A high-precision pattern can be formed on the substrate (film) withoutchanging the size when an organic underlayer film or an organic hardmask is formed on the body to be processed in the inventive patterningprocess.

In addition, in the patterning process, the metal of the body to beprocessed may be silicon, gallium, titanium, tungsten, hafnium,zirconium, chromium, germanium, copper, silver, gold, indium, arsenic,palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or analloy thereof.

Using a body to be processed constituted by such a metal, anegative-type pattern can be transferred to the body to be processedwith high precision by etching precisely.

Advantageous Effects of Invention

The inventive composition for forming a silicon-containing resistunderlayer film contains a betaine-type acid generator, thereby makingit possible to form an upper layer resist pattern excellent in LWR andCDU, and also the inventive composition for forming a silicon-containingresist underlayer film has high etching selectivity relative to anorganic material (organic underlayer film or organic hard mask), so thata formed photoresist pattern can be successively transferred to thesilicon-containing resist underlayer film and the organic underlayerfilm or CVD organic hard mask by dry etching process. In particular, asthe semiconductor-device manufacturing process progresses towardminiaturization recently, multiple exposure process is often used, andthe LWR and CDU in the developed pattern greatly influence the deviceperformances. Hence, it is important to enhance LWR and CDU properties.An upper layer resist pattern excellent in LWR and CDU can be formed byusing the inventive composition for forming a silicon-containing resistunderlayer film. Further, since the inventive composition for forming asilicon-containing resist underlayer film has favorable dry etchingselectivity ratio, it is possible to suppress deformation of an upperlayer resist pattern during dry etching and to transfer the pattern to asubstrate with high precision while maintaining the excellent LWR andCDU, even when the silicon-containing resist underlayer film is used asa dry etching mask.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flow diagram showing the inventive patterning process.

FIG. 2 is a flow diagram showing a different patterning process of thepresent invention.

DESCRIPTION OF EMBODIMENTS

The present invention relates to a composition for forming an underlayerfilm suitable for a resist material and patterning using thecomposition. By a deprotection reaction by acid and/or heat afterexposure, the resist material forms a negative tone pattern where anunexposed part is dissolved and an exposed part is not dissolved byorganic solvent development.

As stated above, development of a composition for forming a resistunderlayer film that makes it possible to form an upper layer resistpattern excellent in LWR and CDU has been required.

To achieve the above object, the present inventors have earnestlystudied and found out that a resist underlayer film formed from acomposition for forming a silicon-containing resist underlayer filmcontaining a thermosetting silicon-containing material having an organicgroup having a silanol group, a hydroxy group, or a carboxy group, or anorganic group generating a silanol group, a hydroxy group, or a carboxygroup by an action of acid and/or heat, and a betaine-type compoundhaving an anion moiety and a cation moiety in one molecule, has alowered contact angle on a surface of the underlayer film in a portionthat comes into contact with the upper layer resist pattern to havefavorable pattern adhesiveness; and that furthermore, LWR and CDU of theupper layer resist can be improved since a diffusion distance of thegenerated acid derived from the betaine-type compound is small. Thus,the present invention has been completed.

That is, the present invention is a composition for forming asilicon-containing resist underlayer film comprising: a thermosettingsilicon-containing material containing any one or more of a repeatingunit shown by the following general formula (Sx−1), a repeating unitshown by the following general formula (Sx−2), and a partial structureshown by the following general formula (Sx−3); and a compound shown bythe following general formula (P−0),

wherein R¹ represents an organic group having one or more silanolgroups, hydroxy groups, or carboxy groups, or an organic group fromwhich a protecting group is eliminated by an action of acid and/or heatto generate one or more silanol groups, hydroxy groups, or carboxygroups; R² and R³ are each independently the same as R¹ or eachrepresent a hydrogen atom or a monovalent substituent having 1 to 30carbon atoms; and R¹⁰⁰ represents a divalent organic group substitutedwith one or more fluorine atoms, R¹⁰¹ and R¹⁰² each independentlyrepresents a linear, branched, or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms optionally substituted with a hetero atom oroptionally interposed by a hetero atom; R¹⁰³ represents a linear,branched, or cyclic divalent hydrocarbon group having 1 to 20 carbonatoms optionally substituted with a hetero atom or optionally interposedby a hetero atom; R¹⁰¹ and R¹⁰², or R¹⁰¹ and R¹⁰³, are optionally bondedto each other to form a ring with a sulfur atom in the formula; and L¹⁰⁴represents a single bond or a linear, branched, or cyclic divalenthydrocarbon group having 1 to 20 carbon atoms optionally substitutedwith a hetero atom or optionally interposed by a hetero atom.

In a negative tone pattern obtained by a solvent development,acid-labile group in a resin forming the pattern is eliminated by anacid generated in exposure, and the amount of hydrophilic groups such ascarboxy groups and phenolic hydroxy groups in the resin increases. As aresult, the pattern surface becomes hydrophilic, and a contact anglewith water becomes small. In accordance with such properties of negativetone patterns, the present inventors have made the contact angle of theunderlayer film surface with water small by the effect of acid that isgenerated in the upper layer resist in an exposed portion to provide anunderlayer film favorable in adhesiveness with the negative tonepattern. However, in fine patterns of recent years, application of aphoto-acid generator having cation and anion structures in one molecule,that is, a betaine structure in an upper layer resist for improvement ofLWR and CDU is also known (JP 2014-225005 A). As a characteristic ofthis structure, a salt compound is formed from molecules when acids aregenerated, possibly forming a giant compound by appearance. As a result,presumably, the generated acids diffuse less. Therefore, since generatedacids diffuse less in upper layer resists of recent years, action on theunderlayer film surface is also lessened, and as a result, influence onchange in contact angle is also lessened, and adhesiveness of negativetone patterns is degraded. Accordingly, there is a method of adding aphoto-acid generator to the underlayer film in order to maintain theadhesiveness of negative tone patterns, but with a conventionalphoto-acid generator, diffusion of generated acids is large, andtherefore, the generated acids diffuse to the upper layer resist,causing degradation of LWR and CDU of the upper layer resist.Accordingly, by using a photo-acid generator with less diffusion ofgenerated acids as the photo-acid generator added for lowering thecontact angle on the underlayer film surface as well, adhesiveness withthe negative tone pattern and LWR or CDU can be improved at the sametime, and this can be extremely effective.

When the inventive composition for forming a silicon-containing resistunderlayer film contains a crosslinking catalyst, the crosslinkingcatalyst can promote siloxane bond formation when a thermosettingpolysiloxane is cured, and a silicon-containing resist underlayer filmcrosslinked at high density can be formed. In this manner, not only isthe diffusion of acid generated from the acid generator of the presentinvention reduced, but it is also possible to inactivate the acidpresent in excess by containing a nitrogen-containing compound having asubstituent that is decomposed by acid. In this way, diffusion of acidto the upper layer resist is suppressed and an upper layer resistpattern excellent in LWR and CDU can be formed.

Furthermore, the inventive composition for forming a silicon-containingresist underlayer film makes it possible to form an upper layer resistpattern with favorable LWR and CDU, and also to form asemiconductor-device pattern on a substrate with high yield because ofexcellent dry etching selectivity relative to an upper layer resist andan underlayer organic film or a CVD carbon film.

Hereinafter, the present invention will be described in detail, but thepresent invention is not limited thereto.

[Composition for Forming Silicon-Containing Resist Underlayer Film]

The inventive composition for forming a silicon-containing resistunderlayer film includes a thermosetting silicon-containing materialcontaining any one or more of a repeating unit shown by the abovegeneral formula (Sx−1), a repeating unit shown by the general formula(Sx−2), and a partial structure shown by the general formula (Sx−3), anda compound shown by the general formula (P−0) as essential components.The composition may contain other components, as necessary, such as acrosslinking catalyst or a nitrogen-containing compound having anacid-decomposable substituent. Hereinafter, these components will bedescribed.

[Thermosetting Silicon-Containing Material]

The inventive thermosetting silicon-containing material (Sx) containsany one or more of a repeating unit shown by the following generalformula (Sx−1), a repeating unit shown by the following general formula(Sx−2), and a partial structure shown by the following general formula(Sx−3).

In the formula, R¹ represents an organic group having one or moresilanol groups, hydroxy groups, or carboxy groups; or R¹ represents anorganic group from which a protecting group is eliminated by an actionof acid and/or heat to generate one or more silanol groups, hydroxygroups, or carboxy groups. R² and R³ are each independently the same asR¹ or each represent a hydrogen atom or a monovalent substituent having1 to 30 carbon atoms.

The above R¹ is not particularly limited as long as it is an organicgroup having one or more silanol groups, hydroxy groups, or carboxygroups, or an organic group from which a protecting group is eliminatedby an action of acid and/or heat to generate one or more of the abovegroups.

Examples of such an R¹ of the thermosetting silicon-containing material(Sx) include the following. Note that, in the following formulae, (Si)is depicted to show a bonding site to Si (same hereinafter).

monovalent organic group having 1 to 30 carbon atoms as R² and R³ can beused alone or in combination of two or more thereof.

Examples of the organic group shown by R² and R³ include methyl, ethyl,vinyl, propyl, cyclopropyl, butyl, cyclobutyl, pentyl, cyclopentyl,hexyl, cyclohexyl, cyclohexenyl, cyclopentylmethyl, heptyl,cyclohexylmethyl, cyclohexenylmethyl, bicyclo[2,2,1]heptyl, octyl,cyclooctyl, cyclohexylethyl, decyl, adamanthyl, dodecyl, phenyl, benzyl,phenethyl, naphthyl, and anthranil, and may be the same or different.

Other examples of the organic group shown by R² and R³ include organicgroups having one or more carbon-oxygen single bonds or carbon-oxygendouble bonds, specifically, organic groups having one or more groupsselected from the group consisting of an ether bond, an ester bond,alkoxy groups, a hydroxy group, and the like. Examples of the organicgroups include ones shown by the following general formula (Sm—R).

(P-Q₁-(Si)_(v1)-Q₂-)_(u)-(T)_(v2)-Q₃-(S₂)_(v3)-Q₄-  (Sm—R)

In the general formula (Sm—R), P represents a hydrogen atom, a cyclicether group, a hydroxy group, an alkoxy group having 1 to 4 carbonatoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or analkylcarbonyl group having 1 to 6 carbon atoms; Q₁, Q₂, Q₃, and Q₄ eachindependently represent —C_(q)H_((2q-p))P_(p-), where P is as definedabove, “p” represents an integer of 0 to 3, and “q” represents aninteger of 0 to 10, provided that q=0 means a single bond; “u”represents an integer of 0 to 3; Si and S₂ each independently represent—O—, —CO—, —OCO—, —COO—, or —OCOO—. v1, v2, and v3 each independentlyrepresent 0 or 1. In addition, T represents a divalent atom other thancarbon, or a divalent group of an alicyclic, aromatic, or heterocyclicring.

As T, examples of the alicyclic, aromatic, or heterocyclic ringoptionally containing a hetero-atom such as an oxygen atom are shownbelow. In T, positions bonded to Q₂ and Q₃ are not particularly limited,and can be selected appropriately in consideration of reactivitydependent on steric factors, availability of commercial reagents used inthe reaction, and so on.

Favorable examples of the organic group having one or more carbon-oxygensingle bonds or carbon-oxygen double bonds in the general formula (Sm—R)include the following.

Moreover, as an example of the organic group of R² and R³, an organicgroup containing a silicon-silicon bond can also be used. Specificexamples thereof include the following.

Further, as an example of the organic group of R² and R³, an organicgroup having a fluorine atom can also be used. Specific examples thereofinclude organic groups obtained from silicon compounds shown fromparagraphs (0059) to (0065) of Japanese Unexamined Patent ApplicationPublication No. 2012-53253.

In the hydrolysable monomer (Sm), one, two, or three among chlorine,bromine, iodine, an acetoxy group, a methoxy group, an ethoxy group, apropoxy group, a butoxy group, and so forth are bonded as a hydrolysablegroup(s) on silicon shown by (Si) in the partial structure.

Furthermore, the silicon-containing material (Sx) of the presentinvention can be produced by hydrolysis condensation of a mixturecontaining the following hydrolysable monomer(s) (Sm).

Specific examples of the hydrolysable monomer (Sm) includetetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,tetraisopropoxysilane, trimethoxysilane, triethoxysilane,tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane,methyltriethoxysilane, methyltripropoxysilane,methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane,propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane,propyltriisopropoxysilane, isopropyltrimethoxysilane,isopropyltriethoxysilane, isopropyltripropoxysilane,isopropyltriisopropoxysilane, butyltrimethoxysilane,butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane,sec-butyltrimethoxysilane, sec-butyltriethoxysilane,sec-butyltripropoxysilane, sec-butyltriisopropoxysilane,t-butyltrimethoxysilane, t-butyltriethoxysilane,t-butyltripropoxysilane, t-butyltriisopropoxysilane,cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane,cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane,cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane,cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane,cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane,cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane,cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane,cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane,cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane,cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane,cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane,cyclopentadienylpropyltrimethoxysilane,cyclopentadienylpropyltriethoxysilane,cyclopentadienylpropyltripropoxysilane,cyclopentadienylpropyltriisopropoxysilane,bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane,bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane,bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane,bicycloheptyltripropoxysilane, bicycloheptyltriisopropoxysilane,adamantyltrimethoxysilane, adamantyltriethoxysilane,adamantyltripropoxysilane, adamantyltriisopropoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane,phenyltriisopropoxysilane, benzyltrimethoxysilane,benzyltriethoxysilane, benzyltripropoxysilane,benzyltriisopropoxysilane, anisyltrimethoxysilane,anisyltriethoxysilane, anisyltripropoxysilane,anisyltriisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane,tolyltripropoxysilane, tolyltriisopropoxysilane,phenethyltrimethoxysilane, phenethyltriethoxysilane,phenethyltripropoxysilane, phenethyltriisopropoxysilane,naphthyltrimethoxysilane, naphthyltriethoxysilane,naphthyltripropoxysilane, naphthyltriisopropoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,methylethyldimethoxysilane, methylethyldiethoxysilane,dimethyldipropoxysilane, dimethyldiisopropoxysilane,diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane,diethyldiisopropoxysilane, dipropyldimethoxysilane,dipropyldiethoxysilane, dipropyldipropoxysilane,dipropyldiisopropoxysilane, diisopropyldimethoxysilane,diisopropyldiethoxysilane, diisopropyldipropoxysilane,diisopropyldiisopropoxysilane, dibutyldimethoxysilane,dibutyldiethoxysilane, dibutyldipropoxysilane,dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane,di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane,di-sec-butyldiisopropoxysilane, di-t-butyldimethoxysilane,di-t-butyldiethoxysilane, di-t-butyldipropoxysilane,di-t-butyldiisopropoxysilane, dicyclopropyldimethoxysilane,dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane,dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane,dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane,dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane,dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane,dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane,dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane,dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane,dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane,dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane,dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane,dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane,dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane,dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane,dicyclopentadienylpropyldiethoxysilane,dicyclopentadienylpropyldipropoxysilane,dicyclopentadienylpropyldiisopropoxysilane,bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis (bicycloheptenyl)dipropoxysilane,bis (bicycloheptenyl)diisopropoxysilane,bis(bicycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane,bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane,diadamantyldimethoxysilane, diadamantyldiethoxysilane,diadamantyldipropoxysilane, diadamantyldiisopropoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane,methylphenyldimethoxysilane, methylphenyldiethoxysilane,diphenyldipropoxysilane, diphenyldiisopropoxysilane,trimethylmethoxysilane, trimethylethoxysilane,dimethylethylmethoxysilane, dimethylethylethoxysilane,dimethylphenylmethoxysilane, dimethylphenylethoxysilane,dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane,dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, and thelike.

Preferable examples of the compound include tetramethoxysilane,tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane,isopropyltrimethoxysilane, isopropyltriethoxysilane,butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane,isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane,cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane,benzyltriethoxysilane, phenethyltrimethoxysilane,phenethyltriethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,methylethyldimethoxysilane, methylethyldiethoxysilane,dipropyldimethoxysilane, dibutyldimethoxysilane,methylphenyldimethoxysilane, methylphenyldiethoxysilane,trimethylmethoxysilane, dimethylethylmethoxysilane,dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane,dimethylphenethylmethoxysilane, and the like.

[Method for Synthesizing Thermosetting Silicon-Containing Material (Sx)]

(Synthesis Method 1: Acid Catalyst)

The thermosetting silicon-containing material of the present invention(Sx: hereinafter, also referred to as thermosetting polysiloxane) can beproduced by hydrolysis condensation of one of the hydrolysable monomers(Sm) or a mixture of two or more kinds thereof (hereinafter, alsoreferred to simply as “monomer”) in the presence of an acid catalyst.

Examples of the acid catalyst used in this event include organic acidssuch as formic acid, acetic acid, oxalic acid, maleic acid,methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid;and inorganic acids such as hydrofluoric acid, hydrochloric acid,hydrobromic acid, sulfuric acid, nitric acid, perchloric acid,phosphoric acid. The catalyst can be used in an amount of 1×10⁻⁶ to 10mol, preferably 1×10⁻⁵ to 5 mol, more preferably 1×10⁻⁴ to 1 mol,relative to 1 mol of the monomer.

When the thermosetting polysiloxane is obtained from these monomers bythe hydrolysis condensation, water is preferably added in an amount of0.01 to 100 mol, more preferably 0.05 to 50 mol, further preferably 0.1to 30 mol, per mol of the hydrolysable substituent bonded to themonomer. When the amount is 100 mol or less, a device used for thereaction can be made small and economical.

As the operation method, the monomer is added to a catalyst aqueoussolution to initiate the hydrolysis condensation reaction. In thisevent, an organic solvent may be added to the catalyst aqueous solution,or the monomer may be diluted with an organic solvent, or both of theseoperations may be performed. The reaction temperature may be 0 to 100°C., preferably 5 to 80° C. As a preferable method, when the monomer isadded dropwise, the temperature is maintained at 5 to 80° C., and thenthe mixture is aged at 20 to 80° C.

The organic solvent which can be added to the catalyst aqueous solutionor with which the monomer can be diluted is preferably methanol,ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene,hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone, methyl amyl ketone, butanediol monomethyl ether,propylene glycol monomethyl ether, ethylene glycol monomethyl ether,butanediol monoethyl ether, propylene glycol monoethyl ether, ethyleneglycol monoethyl ether, propylene glycol dimethyl ether, diethyleneglycol dimethyl ether, propylene glycol monomethyl ether acetate,propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate,methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butylacetate, t-butyl propionate, propylene glycol mono-t-butyl etheracetate, γ-butyrolactone, mixtures thereof, and the like.

Among these solvents, water-soluble solvents are preferable. Examplesthereof include alcohols such as methanol, ethanol, 1-propanol, and2-propanol; polyhydric alcohols such as ethylene glycol and propyleneglycol; polyhydric alcohol condensate derivatives such as butanediolmonomethyl ether, propylene glycol monomethyl ether, ethylene glycolmonomethyl ether, butanediol monoethyl ether, propylene glycol monoethylether, ethylene glycol monoethyl ether, butanediol monopropyl ether,propylene glycol monopropyl ether, and ethylene glycol monopropyl ether;acetone, acetonitrile, tetrahydrofuran, and the like. Among these,particularly preferable is one having a boiling point of 100° C. orless.

Note that the organic solvent is used in an amount of preferably 0 to1,000 ml, particularly preferably 0 to 500 ml, relative to 1 mol of themonomer. When the organic solvent is used in a smaller amount, only asmaller reaction vessel is required and more economical.

Then, if necessary, neutralization reaction of the catalyst is carriedout to obtain a reaction mixture aqueous solution. In this event, theamount of an alkaline substance usable for the neutralization ispreferably 0.1 to 2 equivalents relative to the acid used as thecatalyst. This alkaline substance may be any substance as long as itshows alkalinity in water.

Subsequently, by-products such as alcohol produced by the hydrolysiscondensation reaction are preferably removed from the reaction mixtureby a procedure such as removal under reduced pressure. In this event,the reaction mixture is heated at a temperature of preferably 0 to 100°C., more preferably 10 to 90° C., further preferably 15 to 80° C.,although the temperature depends on the kinds of the added organicsolvent, the alcohol produced in the reaction, and so forth.Additionally, in this event, the degree of vacuum is preferablyatmospheric pressure or less, more preferably 80 kPa or less in absolutepressure, further preferably 50 kPa or less in absolute pressure,although the degree of vacuum varies depending on the kinds of theorganic solvent, alcohol, etc. to be removed, as well as exhaustingequipment, condensation equipment, and heating temperature. In thiscase, it is difficult to accurately know the amount of alcohol to beremoved, but it is desirable to remove about 80 mass % or more of theproduced alcohol, etc.

Next, the acid catalyst used in the hydrolysis condensation may beremoved from the reaction mixture. As a method for removing the acidcatalyst, the thermosetting polysiloxane solution is mixed with water,and the thermosetting polysiloxane is extracted with an organic solvent.Preferably, the organic solvent used in this event is capable ofdissolving the thermosetting polysiloxane and achieves two-layerseparation when mixed with water. Examples of the organic solventinclude methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethylacetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether,propylene glycol monomethyl ether, ethylene glycol monomethyl ether,butanediol monoethyl ether, propylene glycol monoethyl ether, ethyleneglycol monoethyl ether, butanediol monopropyl ether, propylene glycolmonopropyl ether, ethylene glycol monopropyl ether, propylene glycoldimethyl ether, diethylene glycol dimethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propyleneglycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutylketone, cyclopentyl methyl ether, mixtures thereof, and the like.

Further, it is also possible to use a mixture of a water-soluble organicsolvent and a slightly-water-soluble organic solvent. Preferableexamples of the mixture include methanol-ethyl acetate mixture,ethanol-ethyl acetate mixture, 1-propanol-ethyl acetate mixture,2-propanol-ethyl acetate mixture, butanediol monomethyl ether-ethylacetate mixture, propylene glycol monomethyl ether-ethyl acetatemixture, ethylene glycol monomethyl ether-ethyl acetate mixture,butanediol monoethyl ether-ethyl acetate mixture, propylene glycolmonoethyl ether-ethyl acetate mixture, ethylene glycol monoethylether-ethyl acetate mixture, butanediol monopropyl ether-ethyl acetatemixture, propylene glycol monopropyl ether-ethyl acetate mixture,ethylene glycol monopropyl ether-ethyl acetate mixture, methanol-methylisobutyl ketone mixture, ethanol-methyl isobutyl ketone mixture,1-propanol-methyl isobutyl ketone mixture, 2-propanol-methyl isobutylketone mixture, propylene glycol monomethyl ether-methyl isobutyl ketonemixture, ethylene glycol monomethyl ether-methyl isobutyl ketonemixture, propylene glycol monoethyl ether-methyl isobutyl ketonemixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture,propylene glycol monopropyl ether-methyl isobutyl ketone mixture,ethylene glycol monopropyl ether-methyl isobutyl ketone mixture,methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methylether mixture, 1-propanol-cyclopentyl methyl ether mixture,2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethylether-cyclopentyl methyl ether mixture, ethylene glycol monomethylether-cyclopentyl methyl ether mixture, propylene glycol monoethylether-cyclopentyl methyl ether mixture, ethylene glycol monoethylether-cyclopentyl methyl ether mixture, propylene glycol monopropylether-cyclopentyl methyl ether mixture, ethylene glycol monopropylether-cyclopentyl methyl ether mixture, methanol-propylene glycol methylether acetate mixture, ethanol-propylene glycol methyl ether acetatemixture, 1-propanol-propylene glycol methyl ether acetate mixture,2-propanol-propylene glycol methyl ether acetate mixture, propyleneglycol monomethyl ether-propylene glycol methyl ether acetate mixture,ethylene glycol monomethyl ether-propylene glycol methyl ether acetatemixture, propylene glycol monoethyl ether-propylene glycol methyl etheracetate mixture, ethylene glycol monoethyl ether-propylene glycol methylether acetate mixture, propylene glycol monopropyl ether-propyleneglycol methyl ether acetate mixture, ethylene glycol monopropylether-propylene glycol methyl ether acetate mixture, and the like.However, the combination is not limited thereto.

The mixing ratio of the water-soluble organic solvent and theslightly-water-soluble organic solvent is appropriately selected. Theamount of the water-soluble organic solvent may be 0.1 to 1,000 parts bymass, preferably 1 to 500 parts by mass, further preferably 2 to 100parts by mass, based on 100 parts by mass of the slightly-water-solubleorganic solvent.

Subsequently, the thermosetting polysiloxane may be washed with neutralwater. The water which is commonly called deionized water or ultrapurewater may be used. The amount of the water may be 0.01 to 100 L,preferably 0.05 to 50 L, more preferably 0.1 to 5 L, relative to 1 L ofthe thermosetting polysiloxane solution. This washing procedure may beperformed by putting both the thermosetting polysiloxane and water intothe same container, followed by stirring and then leaving to stand toseparate the aqueous layer. The washing may be performed once or more,preferably once to approximately five times because washing ten times ormore does not always produce the full washing effects thereof.

Other methods for removing the acid catalyst include a method using anion-exchange resin, and a method in which the acid catalyst is removedafter neutralization with an epoxy compound such as ethylene oxide andpropylene oxide. These methods can be appropriately selected inaccordance with the acid catalyst used in the reaction.

In this water-washing operation, a part of the thermosettingpolysiloxane escapes into the aqueous layer, so that substantially thesame effect as fractionation operation is obtained in some cases. Hence,the number of water-washing operations and the amount of washing watermay be appropriately determined in view of the catalyst removal effectand the fractionation effect.

To a solution of either the thermosetting polysiloxane with the acidcatalyst still remaining or the thermosetting polysiloxane with the acidcatalyst having been removed, a final solvent may be added for solventexchange under reduced pressure. Thus, a desired thermosettingpolysiloxane solution is obtained. The temperature during this solventexchange is preferably 0 to 100° C., more preferably 10 to 90° C.,further preferably 15 to 80° C., depending on the kinds of the reactionsolvent and the extraction solvent to be removed. Moreover, the degreeof vacuum in this event is preferably atmospheric pressure or less, morepreferably 80 kPa or less in absolute pressure, further preferably 50kPa or less in absolute pressure, although the degree of vacuum variesdepending on the kinds of the extraction solvent to be removed,exhausting equipment, condensation equipment, and heating temperature.

In this event, the thermosetting polysiloxane may become unstable by thesolvent exchange. This occurs due to incompatibility of thethermosetting polysiloxane with the final solvent. Thus, in order toprevent this phenomenon, a monohydric, dihydric, or polyhydric alcoholhaving cyclic ether substituent as shown in paragraphs (0181) to (0182)of JP 2009-126940 A may be added as a stabilizer. The alcohol may beadded in an amount of 0 to 25 parts by mass, preferably 0 to 15 parts bymass, more preferably 0 to 5 parts by mass, based on 100 parts by massof the thermosetting polysiloxane in the solution before the solventexchange. When the alcohol is added, the amount is preferably 0.5 partsby mass or more. If necessary, the monohydric, dihydric, or polyhydricalcohol having cyclic ether substituent may be added to the solution inadvance of the solvent exchange operation, and then the operation isperformed.

If the thermosetting polysiloxane is concentrated above a certainconcentration level, the condensation reaction may further progress, sothat the thermosetting polysiloxane becomes no longer soluble in anorganic solvent. Thus, it is preferable to maintain the solution statewith a proper concentration. Meanwhile, if the concentration is too low,the amount of solvent is excessive. Hence, the solution state with aproper concentration is economical and preferable. The concentration inthis state is preferably 0.1 to 20 mass %.

The final solvent added to the thermosetting polysiloxane solution ispreferably an alcohol-based solvent, particularly preferably monoalkylether derivatives of ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, butanediol, and so on.Specifically, preferable examples thereof include butanediol monomethylether, propylene glycol monomethyl ether, ethylene glycol monomethylether, butanediol monoethyl ether, propylene glycol monoethyl ether,ethylene glycol monoethyl ether, butanediol monopropyl ether, propyleneglycol monopropyl ether, ethylene glycol monopropyl ether, diacetonealcohol, and the like.

When these solvents are used as the main component, a non-alcohol-basedsolvent can also be added as an adjuvant solvent. Examples of theadjuvant solvent include acetone, tetrahydrofuran, toluene, hexane,ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycoldimethyl ether, diethylene glycol dimethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propyleneglycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutylketone, cyclopentyl methyl ether, and the like.

As an alternative reaction operation using an acid catalyst, water or awater-containing organic solvent is added to the monomer or an organicsolution of the monomer to initiate the hydrolysis reaction. In thisevent, the catalyst may be added to the monomer or the organic solutionof the monomer, or may be added to the water or the water-containingorganic solvent. The reaction temperature may be 0 to 100° C.,preferably 10 to 80° C. As a preferable method, when the water is addeddropwise, the mixture is heated to 10 to 50° C., and then further heatedto 20 to 80° C. for aging.

When the organic solvent is used, a water-soluble solvent is preferable.Examples thereof include methanol, ethanol, 1-propanol, 2-propanol,1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran,acetonitrile; polyhydric alcohol condensate derivatives such asbutanediol monomethyl ether, propylene glycol monomethyl ether, ethyleneglycol monomethyl ether, butanediol monoethyl ether, propylene glycolmonoethyl ether, ethylene glycol monoethyl ether, butanediol monopropylether, propylene glycol monopropyl ether, ethylene glycol monopropylether, propylene glycol dimethyl ether, diethylene glycol dimethylether, propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, and propylene glycol monopropyl ether; mixturesthereof, and the like.

The organic solvent is used in an amount of preferably 0 to 1,000 ml,particularly preferably 0 to 500 ml, relative to 1 mol of the monomer.When the organic solvent is used in a small amount, only a smallreaction vessel is required and economical. The obtained reactionmixture may be subjected to post-treatment by the same procedure asmentioned above to obtain a thermosetting polysiloxane.

(Synthesis Method 2: Alkali Catalyst)

Alternatively, the thermosetting silicon-containing material (Sx:thermosetting polysiloxane) can be produced by hydrolysis condensationof one of the hydrolysable monomers (Sm) or a mixture of two or morekinds thereof in the presence of an alkali catalyst. Examples of thealkali catalyst used in this event include methylamine, ethylamine,propylamine, butylamine, ethylenediamine, hexamethylenediamine,dimethylamine, diethylamine, ethylmethylamine, trimethylamine,triethylamine, tripropylamine, tributylamine, cyclohexylamine,dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyl diethanolamine, triethanolamine,diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene,hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine,N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine,picoline, tetramethylammonium hydroxide, choline hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia,lithium hydroxide, sodium hydroxide, potassium hydroxide, bariumhydroxide, calcium hydroxide, and the like. The catalyst can be used inan amount of 1×10⁻⁶ mol to 10 mol, preferably 1×10⁻⁵ mol to 5 mol, morepreferably 1×10⁻⁴ mol to 1 mol, relative to 1 mol of the siliconmonomer.

When the thermosetting polysiloxane is obtained from the monomer by thehydrolysis condensation, water is preferably added in an amount of 0.1to 50 mol per mol of the hydrolysable substituent bonded to the monomer.When the amount is 50 mol or less, a reaction device can be made smalland economical.

As the operation method, the monomer is added to a catalyst aqueoussolution to initiate the hydrolysis condensation reaction. In thisevent, an organic solvent may be added to the catalyst aqueous solution,or the monomer may be diluted with an organic solvent, or both of theseoperations may be performed. The reaction temperature may be 0 to 100°C., preferably 5 to 80° C. As a preferable method, when the monomer isadded dropwise, the temperature is maintained at 5 to 80° C., and thenthe mixture is aged at 20 to 80° C.

As the organic solvent which can be added to the alkali catalyst aqueoussolution or with which the monomer can be diluted, the same organicsolvents exemplified as the organic solvents which can be added to theacid catalyst aqueous solution are preferably used. Note that theorganic solvent is used in an amount of preferably 0 to 1,000 mlrelative to 1 mol of the monomer because the reaction can be performedeconomically.

Then, if necessary, neutralization reaction of the catalyst is carriedout to obtain a reaction mixture aqueous solution. In this event, theamount of an acidic substance usable for the neutralization ispreferably 0.1 to 2 equivalents relative to the alkaline substance usedas the catalyst. This acidic substance may be any substance as long asit shows acidity in water.

Subsequently, by-products such as alcohol produced by the hydrolysiscondensation reaction are desirably removed from the reaction mixture bya procedure such as removal under reduced pressure. In this event, thereaction mixture is heated at a temperature of preferably 0 to 100° C.,more preferably 10 to 90° C., further preferably 15 to 80° C., althoughthe temperature depends on the kinds of the added organic solvent andalcohol produced in the reaction. Moreover, the degree of vacuum in thisevent is preferably atmospheric pressure or less, more preferably 80 kPaor less in absolute pressure, further preferably 50 kPa or less inabsolute pressure, although the degree of vacuum varies depending on thekinds of the organic solvent and alcohol to be removed, as well asexhausting equipment, condensation equipment, and heating temperature.In this case, it is difficult to accurately know the amount of alcoholto be removed, but it is desirable to remove about 80 mass % or more ofthe produced alcohol.

Next, to remove the catalyst used in the hydrolysis condensation, thethermosetting polysiloxane may be extracted with an organic solvent.Preferably, the organic solvent used in this event is capable ofdissolving the thermosetting polysiloxane and achieves two-layerseparation when mixed with water. Examples of the organic solventinclude methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethylacetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethylether, ethylene glycol monomethyl ether, propylene glycol monoethylether, ethylene glycol monoethyl ether, propylene glycol monopropylether, ethylene glycol monopropyl ether, propylene glycol dimethylether, diethylene glycol dimethyl ether, propylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate,butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate,t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl etheracetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methylether, mixtures thereof, and the like.

Next, to remove the alkali catalyst used in the hydrolysis condensation,the thermosetting polysiloxane may be extracted with an organic solvent.Preferably, the organic solvent used in this event is capable ofdissolving the thermosetting polysiloxane and achieves two-layerseparation when mixed with water. Further, a mixture of a water-solubleorganic solvent and a slightly-water-soluble organic solvent can also beused.

As concrete examples of the organic solvent used for removing the alkalicatalyst, it is possible to use the aforementioned organic solventsspecifically exemplified for the acid catalyst removal or the samemixtures of the water-soluble organic solvent and theslightly-water-soluble organic solvent.

Although the mixing ratio of the water-soluble organic solvent and theslightly-water-soluble organic solvent is appropriately selected, theamount of the water-soluble organic solvent may be 0.1 to 1,000 parts bymass, preferably 1 to 500 parts by mass, further preferably 2 to 100parts by mass, based on 100 parts by mass of the slightly-water-solubleorganic solvent.

Subsequently, the thermosetting polysiloxane may be washed with neutralwater. As the water, what is commonly called deionized water orultrapure water may be used. The amount of the water may be 0.01 to 100L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L, relative to 1 Lof the thermosetting polysiloxane solution. This washing procedure maybe performed by putting both the thermosetting polysiloxane and waterinto the same container, followed by stirring and then leaving to standto separate the aqueous layer. The washing may be performed once ormore, preferably once to approximately five times because washing tentimes or more does not always produce the full washing effects thereof.

To the washed thermosetting polysiloxane solution, a final solvent maybe added for solvent exchange under reduced pressure. Thus, a desiredthermosetting polysiloxane solution is obtained. The temperature duringthis solvent exchange is preferably 0 to 100° C., more preferably 10 to90° C., further preferably 15 to 80° C., depending on the kind of theextraction solvent to be removed. Moreover, the degree of vacuum in thisevent is preferably atmospheric pressure or less, more preferably 80 kPaor less in absolute pressure, further preferably 50 kPa or less inabsolute pressure, although the degree of vacuum varies depending on thekinds of the extraction solvent to be removed, exhausting equipment,condensation equipment, and heating temperature.

The final solvent added to the thermosetting polysiloxane solution ispreferably an alcohol-based solvent, particularly preferably a monoalkylether of ethylene glycol, diethylene glycol, triethylene glycol, etc.and a monoalkyl ether of propylene glycol, dipropylene glycol, etc.Specifically, preferable examples thereof include propylene glycolmonomethyl ether, ethylene glycol monomethyl ether, propylene glycolmonoethyl ether, ethylene glycol monoethyl ether, propylene glycolmonopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol,and the like.

As an alternative reaction operation using an alkali catalyst, water ora water-containing organic solvent is added to the monomer or an organicsolution of the monomer to initiate the hydrolysis reaction. In thisevent, the catalyst may be added to the monomer or the organic solutionof the monomer, or may be added to the water or the water-containingorganic solvent. The reaction temperature may be 0 to 100° C.,preferably 10 to 80° C. As a preferable method, when the water is addeddropwise, the mixture is heated to 10 to 50° C., and then further heatedto 20 to 80° C. for the aging.

The organic solvent usable for the organic solution of the monomer orthe water-containing organic solvent is preferably a water-solublesolvent. Examples thereof include methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone,tetrahydrofuran, acetonitrile; polyhydric alcohol condensate derivativessuch as propylene glycol monomethyl ether, ethylene glycol monomethylether, propylene glycol monoethyl ether, ethylene glycol monoethylether, propylene glycol monopropyl ether, ethylene glycol monopropylether, propylene glycol dimethyl ether, diethylene glycol dimethylether, propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, and propylene glycol monopropyl ether; mixturesthereof, and the like.

The molecular weight of the thermosetting polysiloxane obtained by theabove synthesis method 1 or 2 can be adjusted not only through theselection of the monomer but also by controlling the reaction conditionsduring the polymerization, and it is preferable to use the thermosettingpolysiloxane having a weight average molecular weight (Mw) of 100,000 orless, more preferably 200 to 50,000, further preferably 300 to 30,000.When a thermosetting polysiloxane has a weight average molecular weightof 100,000 or less, generation of foreign matters and coating spots donot occur.

Regarding data on the weight average molecular weight, the molecularweight is expressed in terms of polystyrene which is obtained bygel-permeation chromatography (GPC) using a refractive index (RI)detector, tetrahydrofuran as an eluent, and polystyrene as a referencesubstance.

Properties of the thermosetting polysiloxane used in the presentinvention vary depending on the kind of the acid or alkali catalyst usedin the hydrolysis condensation and the reaction conditions. Thus, thecatalyst and the reaction conditions can be appropriately selected inaccordance with the characteristics of a resist underlayer film to beachieved.

Furthermore, a polysiloxane derivative produced from a mixture of thesemonomers with a hydrolysable metal compound shown by the followinggeneral formula (Mm) under the conditions using the acid or alkalicatalyst can be used as a component of a composition for forming aresist underlayer film.

U(OR⁷)_(m7)(OR⁸)_(m8)  (Mm)

In the formula, R⁷ and R⁸ each represent an organic group having 1 to 30carbon atoms; m7+m8 represents the same number as a valence determinedby the kind of U; m7 and m8 each represent an integer of 0 or more; andU represents an element belonging to the group III, IV, or V in theperiodic table, except for carbon and silicon.

Examples of the hydrolysable metal compound (Mm) used in this eventinclude the following.

When U is boron, examples of the compound shown by the general formula(Mm) include, as monomers, boron methoxide, boron ethoxide, boronpropoxide, boron butoxide, boron amyloxide, boron hexyloxide, boroncyclopentoxide, boron cyclohexyloxide, boron allyloxide, boronphenoxide, boron methoxyethoxide, boric acid, boron oxide, and the like.

When U is aluminum, examples of the compound shown by the generalformula (Mm) include, as monomers, aluminum methoxide, aluminumethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide,aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide,aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide,aluminum ethoxyethoxide, aluminum dipropoxy(ethyl acetoacetate),aluminum dibutoxy(ethyl acetoacetate), aluminum propoxy bis(ethylacetoacetate), aluminum butoxy bis(ethyl acetoacetate), aluminum2,4-pentanedionate, aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, andthe like.

When U is gallium, examples of the compound shown by the general formula(Mm) include, as monomers, gallium methoxide, gallium ethoxide, galliumpropoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide,gallium cyclopentoxide, gallium cyclohexyloxide, gallium allyloxide,gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide,gallium dipropoxy(ethyl acetoacetate), gallium dibutoxy(ethylacetoacetate), gallium propoxy bis(ethyl acetoacetate), gallium butoxybis(ethyl acetoacetate), gallium 2,4-pentanedionate, gallium2,2,6,6-tetramethyl-3,5-heptanedionate, and the like.

When U is yttrium, examples of the compound shown by the general formula(Mm) include, as monomers, yttrium methoxide, yttrium ethoxide, yttriumpropoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide,yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium allyloxide,yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide,yttrium dipropoxy(ethyl acetoacetate), yttrium dibutoxy(ethylacetoacetate), yttrium propoxy bis(ethyl acetoacetate), yttrium butoxybis(ethyl acetoacetate), yttrium 2,4-pentanedionate, yttrium2,2,6,6-tetramethyl-3,5-heptanedionate, and the like.

When U is germanium, examples of the compound shown by the generalformula (Mm) include, as monomers, germanium methoxide, germaniumethoxide, germanium propoxide, germanium butoxide, germanium amyloxide,germanium hexyloxide, germanium cyclopentoxide, germaniumcyclohexyloxide, germanium allyloxide, germanium phenoxide, germaniummethoxyethoxide, germanium ethoxyethoxide, and the like.

When U is titanium, examples of the compound shown by the generalformula (Mm) include, as monomers, titanium methoxide, titaniumethoxide, titanium propoxide, titanium butoxide, titanium amyloxide,titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide,titanium allyloxide, titanium phenoxide, titanium methoxyethoxide,titanium ethoxyethoxide, titanium dipropoxy bis(ethyl acetoacetate),titanium dibutoxy bis(ethyl acetoacetate), titanium dipropoxybis(2,4-pentanedionate), titanium dibutoxy bis(2,4-pentanedionate), andthe like.

When U is hafnium, examples of the compound shown by the general formula(Mm) include, as monomers, hafnium methoxide, hafnium ethoxide, hafniumpropoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide,hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium allyloxide,hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide,hafnium dipropoxy bis (ethyl acetoacetate), hafnium dibutoxy bis(ethylacetoacetate), hafnium dipropoxy bis (2,4-pentanedionate), hafniumdibutoxy bis(2,4-pentanedionate), and the like.

When U is tin, examples of the compound shown by the general formula(Mm) include, as monomers, methoxy tin, ethoxy tin, propoxy tin, butoxytin, phenoxy tin, methoxyethoxy tin, ethoxyethoxy tin, tin2,4-pentanedionate, tin 2,2,6,6-tetramethyl-3,5-heptanedionate, and thelike.

When U is arsenic, examples of the compound shown by the general formula(Mm) include, as monomers, methoxy arsenic, ethoxy arsenic, propoxyarsenic, butoxy arsenic, phenoxy arsenic, and the like.

When U is antimony, examples of the compound shown by the generalformula (Mm) include, as monomers, methoxy antimony, ethoxy antimony,propoxy antimony, butoxy antimony, phenoxy antimony, antimony acetate,antimony propionate, and the like.

When U is niobium, examples of the compound shown by the general formula(Mm) include, as monomers, methoxy niobium, ethoxy niobium, propoxyniobium, butoxy niobium, phenoxy niobium, and the like.

When U is tantalum, examples of the compound shown by the generalformula (Mm) include, as monomers, methoxy tantalum, ethoxy tantalum,propoxy tantalum, butoxy tantalum, phenoxy tantalum, and the like.

When U is bismuth, examples of the compound shown by the general formula(Mm) include, as monomers, methoxy bismuth, ethoxy bismuth, propoxybismuth, butoxy bismuth, phenoxy bismuth, and the like.

When U is phosphorus, examples of the compound shown by the generalformula (Mm) include, as monomers, trimethyl phosphate, triethylphosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite,tripropyl phosphite, diphosphorous pentaoxide, and the like.

When U is vanadium, examples of the compound shown by the generalformula (Mm) include, as monomers, vanadium oxidebis(2,4-pentanedionate), vanadium 2,4-pentanedionate, vanadiumtributoxide oxide, vanadium tripropoxide oxide, and the like.

When U is zirconium, examples of the compound shown by the generalformula (Mm) include, as monomers, methoxy zirconium, ethoxy zirconium,propoxy zirconium, butoxy zirconium, phenoxy zirconium, zirconiumdibutoxide bis(2,4-pentanedionate), zirconium dipropoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate), and the like.

[Betaine-Type Compound]

The inventive composition for forming a silicon-containing resistunderlayer film contains a betaine-type compound (acid generator), whichhas a cation moiety and a anion moiety in a molecule, shown by thefollowing general formula (P−0) in addition to the thermosettingsilicon-containing material (Sx). Note that hereinafter, the compound isalso referred to as a photo-acid generator.

where in the formula (P−0), R¹⁰⁰ represents a divalent organic groupsubstituted with one or more fluorine atoms, R¹⁰¹ and R¹⁰² eachindependently represents a linear, branched, or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms optionally substitutedwith a hetero atom or optionally interposed by a hetero atom; R¹⁰³represents a linear, branched, or cyclic divalent hydrocarbon grouphaving 1 to 20 carbon atoms optionally substituted with a hetero atom oroptionally interposed by a hetero atom; R¹⁰¹ and R¹⁰², or R¹⁰¹ and R¹⁰³,are optionally bonded to each other to form a ring with a sulfur atom inthe formula; and L¹⁰⁴ represents a single bond or a linear, branched, orcyclic divalent hydrocarbon group having 1 to 20 carbon atoms optionallysubstituted with a hetero atom or optionally interposed by a heteroatom.

In the general formula (P−0), R¹⁰⁰ may be a linear, branched, or cyclicdivalent hydrocarbon group such as an alkylene group, an alkenylenegroup, and an arylene group having 1 to 20 carbon atoms substituted withone or more fluorine atoms.

Specific examples of R¹⁰⁰ include the following. Note that in thefollowing formulae, parts of the general formula (P−0) other than R¹⁰⁰and “SO₃ ⁻” will be expressed as R²⁰⁰ for convenience.

R¹⁰¹ and R¹⁰² each independently represents a linear, branched, orcyclic monovalent hydrocarbon group such as an alkyl group, an alkenylgroup, an aryl group, and an aralkyl group having 1 to 20 carbon atomsoptionally substituted with a hetero atom or optionally interposed by ahetero atom. As specific R¹⁰¹ and R¹⁰², examples of the alkyl groupinclude a methyl group, an ethyl group, a propyl group, an isopropylgroup, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a cyclopentylgroup, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethylgroup, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornylgroup, an adamantyl group, and the like. Examples of the alkenyl groupinclude a vinyl group, an allyl group, a propenyl group, a butenylgroup, a hexenyl group, a cyclohexenyl group, and the like. Examples ofthe oxoalkyl group include a 2-oxocyclopentyl group, a 2-oxocyclohexylgroup, a 2-oxopropyl group, a 2-oxoethyl group, a2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, a2-(4-methylcyclohexyl)-2-oxoethyl group, and the like. Examples of thearyl group include a phenyl group, a naphthyl group, a thienyl group,and the like; a 4-hydroxyphenyl group; alkoxyphenyl groups such as a4-methoxyphenyl group, a 3-methoxyphenyl group, a 2-methoxyphenyl group,a 4-ethoxyphenyl group, a 4-tert-butoxyphenyl group, and a3-tert-butoxyphenyl group; alkylphenyl groups such as a 2-methylphenylgroup, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenylgroup, a 4-tert-butylphenyl group, a 4-n-butylphenyl group, and a2,4-dimethylphenyl group; alkylnaphthyl groups such as a methylnaphthylgroup and an ethylnaphthyl group; alkoxynaphthyl groups such as amethoxynaphthyl group, an ethoxynaphthyl group, an n-propoxynaphthylgroup, and an n-butoxynaphthyl group; dialkylnaphthyl groups such as adimethylnaphthyl group and a diethylnaphthyl group; dialkoxynaphthylgroups such as a dimethoxynaphthyl group and a diethoxynaphthyl group;and the like. Examples of the aralkyl group include a benzyl group, a1-phenylethyl group, a 2-phenylethyl group, and the like. Examples ofthe aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as a2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a2-(2-naphthyl)-2-oxoethyl group; and the like.

Additionally, R¹⁰¹ and R¹⁰² may be bonded to each other to form a ringtogether with the sulfur atom in the formula; in this case, examples ofthe ring include groups shown by the following formulae.

(a dotted line represents a bond)

In the general formula (P−0), R¹⁰³ represents a linear, branched, orcyclic divalent hydrocarbon group having 1 to 20 carbon atoms optionallysubstituted with a hetero-atom or optionally interposed by ahetero-atom. Specific examples of R¹⁰³ include linear alkanediyl groupssuch as a methylene group, an ethylene group, a propane-1,3-diyl group,a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diylgroup, a heptane-1,7-diyl group, an octane-1,8-diyl group, anonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diylgroup, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, atetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, ahexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; saturatedcyclic hydrocarbon groups such as a cyclopentanediyl group, acyclohexanediyl group, a norbornanediyl group, and an adamantanediylgroup; and unsaturated cyclic hydrocarbon groups such as a phenylenegroup and a naphthylene group. Additionally, some of the hydrogen atomsof these groups may be substituted with an alkyl group such as a methylgroup, an ethyl group, a propyl group, an n-butyl group, and atert-butyl group. Alternatively, some of these groups may be partlysubstituted with a hetero-atom such as an oxygen atom, a sulfur atom, anitrogen atom, and a halogen atom. As a result, a hydroxy group, a cyanogroup, a carbonyl group, an ether bond, an ester bond, a sulfonic acidester bond, a carbonate bond, a lactone ring, a sultone ring, carboxylicanhydride, a haloalkyl group, or the like may be formed.

Further, R¹⁰¹ and R¹⁰³ may be bonded to each other to form a ringtogether with the sulfur atom in the formula; in this case, examples ofthe ring include groups shown by the following formulae.

(a dotted line represents a bond)

In the general formula (P−0), L¹⁰⁴ represents a single bond or a linear,branched, or cyclic divalent hydrocarbon group having 1 to 20 carbonatoms optionally substituted with a hetero-atom or optionally interposedby a hetero-atom. Specific examples of L¹⁰⁴ include linear alkanediylgroups such as a methylene group, an ethylene group, a propane-1,3-diylgroup, a butane-1,4-diyl group, a pentane-1,5-diyl group, ahexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diylgroup, a nonane-1,9-diyl group, a decane-1,10-diyl group, anundecane-1,11-diyl group, a dodecane-1,12-diyl group, atridecane-1,13-diyl group, a tetradecane-1,14-diyl group, apentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and aheptadecane-1,17-diyl group; saturated cyclic hydrocarbon groups such asa cyclopentanediyl group, a cyclohexanediyl group, a norbornanediylgroup, and an adamantanediyl group; and unsaturated cyclic hydrocarbongroups such as a phenylene group and a naphthylene group. Additionally,some of the hydrogen atoms of these groups may be substituted with analkyl group such as a methyl group, an ethyl group, a propyl group, ann-butyl group, and a tert-butyl group. Alternatively, some of thesegroups may be partly substituted with a hetero-atom such as an oxygenatom, a sulfur atom, a nitrogen atom, and a halogen atom. As a result, ahydroxy group, a cyano group, a carbonyl group, an ether bond, an esterbond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, asultone ring, carboxylic anhydride, a haloalkyl group, or the like maybe formed.

The compound (photo-acid generator) shown by the general formula (P−0)is preferably shown by the following general formula (P−1).

In the general formula (P−1), X¹⁰⁵ and X¹⁰⁶ each independently representany of a hydrogen atom, a fluorine atom, and a trifluoromethyl group.n¹⁰⁷ represents an integer of 1 to 4.

The photo-acid generator shown by the general formula (P−0) or (P−1) ismore preferably shown by the following general formula (P−1-1).

In the general formula (P−1-1), R¹⁰⁸, R¹⁰⁹ and R¹¹⁰ each independentlyrepresent a hydrogen atom or a linear, branched, or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms optionally interposed by ahetero-atom. Specific examples of the monovalent hydrocarbon groupinclude a methyl group, an ethyl group, a propyl group, an isopropylgroup, an n-butyl group, a sec-butyl group, a tert-butyl group, atert-amyl group, an n-pentyl group, an n-hexyl group, an n-octyl group,an n-nonyl group, an n-decyl group, a cyclopentyl group, a cyclohexylgroup, a 2-ethylhexyl group, a cyclopentylmethyl group, acyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethylgroup, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornylgroup, an oxanorbornyl group, a tricyclo[5.2.1.0^(2,6)]decanyl group, anadamantyl group, and the like. Additionally, some of hydrogen atoms ofthese groups may be substituted with a hetero-atom such as an oxygenatom, a sulfur atom, a nitrogen atom, and a halogen atom. Alternatively,the monovalent hydrocarbon group may be interposed by a hetero-atom suchas an oxygen atom, a sulfur atom, and a nitrogen atom. As a result, themonovalent hydrocarbon group may be formed to have or interposed by ahydroxy group, a cyano group, a carbonyl group, an ether bond, an esterbond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, asultone ring, carboxylic anhydride, a haloalkyl group, or the like. Themonovalent hydrocarbon group is preferably a methyl group, a methoxygroup, a tert-butyl group, or a tert-butoxy group.

In the general formula (P−1-1), n¹⁰⁸ and n¹⁰⁹ each represent an integerof 0 to 5, preferably 0 or 1. n¹¹⁰ represents an integer of 0 to 4,preferably 0 or 2. L¹⁰⁴, X¹⁰⁵, X¹⁰⁶, and n¹⁰⁷ are as have been describedin detail above.

The photo-acid generator shown by the general formula (P−0), (P−1), or(P−1-1) is further preferably shown by the following general formula(P−1-2).

In the general formula (P−1-2), A¹¹¹ represents a hydrogen atom or atrifluoromethyl group. R¹⁰⁸, R¹⁰⁹, R¹¹⁰, n¹⁰⁸, n¹⁰⁹, n¹¹⁰, and L¹⁰⁴ areas have been described in detail above.

More specific examples of the photo-acid generators shown by the generalformulae (P−0), (P−1), (P−1-1), and (P−1-2) include ones with structuresshown below. However, the present invention is not limited thereto.

The compound shown by (P−0) can be added in an amount of 0.001 to 40parts by mass, preferably 0.1 to 40 parts by mass, further preferably0.1 to 20 parts by mass, based on 100 parts by mass of a thermosettingsilicon-containing material (Sx: thermally crosslinkable polysiloxaneresin). This range is preferable because favorable resolution isobtained and no problem of foreign matters will arise after resistdevelopment or during removal. Further, as necessary, one kind of (P−0)can be used alone, or two or more kinds thereof can be used incombination.

[Other Components]

(Crosslinking Catalyst)

In the present invention, a crosslinking catalyst (Xc) may further beblended into the composition for forming a silicon-containing resistunderlayer film.

The crosslinking catalyst that may be contained in the inventivecomposition for forming a silicon-containing resist underlayer film canpromote siloxane bond formation when a thermosetting polysiloxane iscured, and a silicon-containing resist underlayer film crosslinked athigh density can be formed. In this manner, not only is the diffusion ofacid generated from the acid generator of the present invention reduced,it is also possible to inactivate the acid that exists in excess bycontaining a nitrogen-containing compound having a substituent that isdecomposed by acid and in this way, diffusion of acid to the upper layerresist is suppressed and an upper layer resist pattern excellent in LWRand CDU can be formed.

An example of the blendable crosslinking catalyst includes a compoundshown by the following general formula (Xc0):

L_(a)H_(b)A  (Xc0)

where L represents lithium, sodium, potassium, rubidium, cesium,sulfonium, iodonium, phosphonium, or ammonium; H represents hydrogen; Arepresents a non-nucleophilic counter ion; “a” represents an integer of1 or more; “b” represents an integer of 0 or 1 or more; and a+brepresents a valence of the non-nucleophilic counter ion.

Examples of the crosslinking catalyst used in the present invention asspecific (Xc0) include a sulfonium salt of the following general formula(Xc-1), an iodonium salt of the following general formula (Xc-2), aphosphonium salt of the following general formula (Xc-3), an ammoniumsalt of the following general formula (Xc-4), an alkaline metal salt,and the like.

Examples of the sulfonium salt (Xc-1), the iodonium salt (Xc-2), and thephosphonium salt (Xc-3) are shown below.

Moreover, an example of the ammonium salt (Xc-4) is shown below.

In the formulae, R²¹⁴, R²⁰³, R²⁰⁶, and R²⁰⁷ each represent a linear,branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, oroxoalkenyl group having 1 to 12 carbon atoms, a substituted orunsubstituted aryl group having 6 to 20 carbon atoms, or an aralkylgroup or aryloxoalkyl group having 7 to 12 carbon atoms; some or all ofthe hydrogen atoms of these groups are optionally substituted with analkoxy group or the like. Additionally, R²⁰⁵ and R²⁰⁶ may form a ring;when a ring is formed, R²⁰⁵ and R²⁰⁶ each represent an alkylene grouphaving 1 to 6 carbon atoms. A⁻ represents a non-nucleophilic counterion. R²⁰⁸, R²⁰⁹, R²¹⁰, and R²¹¹ are the same as R²⁰⁴, R²⁰⁵, R²⁰⁶, andR²⁰⁷, and may be each a hydrogen atom. R²⁰⁸ and R²⁰⁹, or R²⁰⁸ and R²⁰⁹and R²¹⁰, may form a ring; when a ring is formed, R²⁰⁸ and R²⁰⁹, or R²⁰⁸and R²⁰⁹ and R²¹⁰, represent an alkylene group having 3 to 10 carbonatoms.

R²⁰⁴, R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹, R²¹⁰, and R²¹¹ may be identical toor different from one another. Specific examples thereof include alkylgroups such as a methyl group, an ethyl group, a propyl group, anisopropyl group, an n-butyl group, a sec-butyl group, a tert-butylgroup, a pentyl group, a hexyl group, a heptyl group, and an octylgroup; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, acyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethylgroup, a norbornyl group, an adamantyl group, and the like. Examples ofthe alkenyl group include a vinyl group, an allyl group, a propenylgroup, a butenyl group, a hexenyl group, a cyclohexenyl group, and thelike. Examples of the oxoalkyl group include a 2-oxocyclopentyl group, a2-oxocyclohexyl group, and the like, and also include a 2-oxopropylgroup, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethylgroup, a 2-(4-methylcyclohexyl)-2-oxoethyl group, and the like. Examplesof the aryl group include a phenyl group, a naphthyl group, and thelike; alkoxyphenyl groups such as a p-methoxyphenyl group, am-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group,a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group;alkylphenyl groups such as a 2-methylphenyl group, a 3-methylphenylgroup, a 4-methylphenyl group, an ethylphenyl group, a4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenylgroup; alkylnaphthyl groups such as a methylnaphthyl group and anethylnaphthyl group; alkoxynaphthyl groups such as a methoxynaphthylgroup and an ethoxynaphthyl group; dialkylnaphthyl groups such as adimethylnaphthyl group and a diethylnaphthyl group; dialkoxynaphthylgroups such as a dimethoxynaphthyl group and a diethoxynaphthyl group;and the like. Examples of the aralkyl group include a benzyl group, aphenylethyl group, a phenethyl group, and the like. Examples of thearyloxoalkyl group include 2-aryl-2-oxoethyl groups such as a2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a2-(2-naphthyl)-2-oxoethyl group; and the like.

Examples of the non-nucleophilic counter ion A-include monovalent ionssuch as hydroxide ion, formate ion, acetate ion, propionate ion,butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoateion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleateion, linolenate ion, benzoate ion, phthalate ion, isophthalate ion,terephthalate ion, salicylate ion, trifluoroacetate ion,monochloroacetate ion, dichloroacetate ion, trichloroacetate ion,fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion,nitrite ion, chlorate ion, bromate ion, methanesulfonate ion,paratoluenesulfonate ion, and monomethylsulfate ion; monovalent ordivalent ions such as oxalate ion, malonate ion, methylmalonate ion,ethylmalonate ion, propylmalonate ion, butylmalonate ion,dimethylmalonate ion, diethylmalonate ion, succinate ion,methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleateion, fumarate ion, citraconate ion, citrate ion, carbonate ion, sulfateion, and the like.

Examples of the alkaline metal salt include salts of lithium, sodium,potassium, cesium, magnesium, and calcium; monovalent salts such ashydroxide, formate, acetate, propionate, butanoate, pentanoate,hexanoate, heptanoate, octanoate, nonanoate, decanoate, oleate,stearate, linoleate, linolenate, benzoate, phthalate, isophthalate,terephthalate, salicylate, trifluoroacetate, monochloroacetate,dichloroacetate, and trichloroacetate; monovalent or divalent salts suchas oxalate, malonate, methylmalonate, ethylmalonate, propylmalonate,butylmalonate, dimethylmalonate, diethylmalonate, succinate,methylsuccinate, glutarate, adipate, itaconate, maleate, fumarate,citraconate, citrate, carbonate, and the like.

Specific examples of the sulfonium salt (Xc-1) includetriphenylsulfonium formate, triphenylsulfonium acetate,triphenylsulfonium propionate, triphenylsulfonium butanoate,triphenylsulfonium benzoate, triphenylsulfonium phthalate,triphenylsulfonium isophthalate, triphenylsulfonium terephthalate,triphenylsulfonium salicylate, triphenylsulfoniumtrifluoromethanesulfonate, triphenylsulfonium trifluoroacetate,triphenylsulfonium monochloroacetate, triphenylsulfoniumdichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfoniumhydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride,triphenylsulfonium bromide, triphenylsulfonium oxalate,triphenylsulfonium malonate, triphenylsulfonium methylmalonate,triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate,triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate,triphenylsulfonium diethylmalonate, triphenylsulfonium succinate,triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate,triphenylsulfonium adipate, triphenylsulfonium itaconate,triphenylsulfonium maleate, triphenylsulfonium fumarate,triphenylsulfonium citraconate, triphenylsulfonium citrate,triphenylsulfonium carbonate, bistriphenylsulfonium oxalate,bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate,bistriphenylsulfonium citraconate, bistriphenylsulfonium citrate,bistriphenylsulfonium carbonate, and the like.

Specific examples of the iodonium salt (Xc-2) include diphenyliodoniumformate, diphenyliodonium acetate, diphenyliodonium propionate,diphenyliodonium butanoate, diphenyliodonium benzoate, diphenyliodoniumphthalate, diphenyliodonium isophthalate, diphenyliodoniumterephthalate, diphenyliodonium salicylate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodonium trifluoroacetate,diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate,diphenyliodonium trichloroacetate, diphenyliodonium hydroxide,diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodoniumbromide, diphenyliodonium iodide, diphenyliodonium oxalate,diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodoniumcitraconate, diphenyliodonium citrate, diphenyliodonium carbonate,bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate,bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconate,bisdiphenyliodonium citrate, bisdiphenyliodonium carbonate, and thelike.

Specific examples of the phosphonium salt (Xc-3) includetetraethylphosphonium formate, tetraethylphosphonium acetate,tetraethylphosphonium propionate, tetraethylphosphonium butanoate,tetraethylphosphonium benzoate, tetraethylphosphonium phthalate,tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate,tetraethylphosphonium salicylate, tetraethylphosphoniumtrifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate,tetraethylphosphonium monochloroacetate, tetraethylphosphoniumdichloroacetate, tetraethylphosphonium trichloroacetate,tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate,tetraethylphosphonium chloride, tetraethylphosphonium bromide,tetraethylphosphonium iodide, tetraethylphosphonium oxalate,tetraethylphosphonium maleate, tetraethylphosphonium fumarate,tetraethylphosphonium citraconate, tetraethylphosphonium citrate,tetraethylphosphonium carbonate, bistetraethylphosphonium oxalate,bistetraethylphosphonium maleate, bistetraethylphosphonium fumarate,bistetraethylphosphonium citraconate, bistetraethylphosphonium citrate,bistetraethylphosphonium carbonate, tetraphenylphosphonium formate,tetraphenylphosphonium acetate, tetraphenylphosphonium propionate,tetraphenylphosphonium butanoate, tetraphenylphosphonium benzoate,tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate,tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate,tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphoniumtrifluoroacetate, tetraphenylphosphonium monochloroacetate,tetraphenylphosphonium dichloroacetate, tetraphenylphosphoniumtrichloroacetate, tetraphenylphosphonium hydroxide,tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride,tetraphenylphosphonium bromide, tetraphenylphosphonium iodide,tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate,tetraphenylphosphonium fumarate, tetraphenylphosphonium citraconate,tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate,bistetraphenylphosphonium oxalate, bistetraphenylphosphonium maleate,bistetraphenylphosphonium fumarate, bistetraphenylphosphoniumcitraconate, bistetraphenylphosphonium citrate,bistetraphenylphosphonium carbonate, and the like.

Meanwhile, specific examples of the ammonium salt (Xc-4) includetetramethylammonium formate, tetramethylammonium acetate,tetramethylammonium propionate, tetramethylammonium butanoate,tetramethylammonium benzoate, tetramethylammonium phthalate,tetramethylammonium isophthalate, tetramethylammonium terephthalate,tetramethylammonium salicylate, tetramethylammoniumtrifluoromethanesulfonate, tetramethylammonium trifluoroacetate,tetramethylammonium monochloroacetate, tetramethylammoniumdichloroacetate, tetramethylammonium trichloroacetate,tetramethylammonium hydroxide, tetramethylammonium nitrate,tetramethylammonium chloride, tetramethylammonium bromide,tetramethylammonium iodide, tetramethylammonium monomethylsulfate,tetramethylammonium oxalate, tetramethylammonium malonate,tetramethylammonium maleate, tetramethylammonium fumarate,tetramethylammonium citraconate, tetramethylammonium citrate,tetramethylammonium carbonate, bistetramethylammonium oxalate,bistetramethylammonium malonate, bistetramethylammonium maleate,bistetramethylammonium fumarate, bistetramethylammonium citraconate,bistetramethylammonium citrate, bistetramethylammonium carbonate,tetraethylammonium formate, tetraethylammonium acetate,tetraethylammonium propionate, tetraethylammonium butanoate,tetraethylammonium benzoate, tetraethylammonium phthalate,tetraethylammonium isophthalate, tetraethylammonium terephthalate,tetraethylammonium salicylate, tetraethylammoniumtrifluoromethanesulfonate, tetraethylammonium trifluoroacetate,tetraethylammonium monochloroacetate, tetraethylammoniumdichloroacetate, tetraethylammonium trichloroacetate, tetraethylammoniumhydroxide, tetraethylammonium nitrate, tetraethylammonium chloride,tetraethylammonium bromide, tetraethylammonium iodide,tetraethylammonium monomethylsulfate, tetraethylammonium oxalate,tetraethylammonium malonate, tetraethylammonium maleate,tetraethylammonium fumarate, tetraethylammonium citraconate,tetraethylammonium citrate, tetraethylammonium carbonate,bistetraethylammonium oxalate, bistetraethylammonium malonate,bistetraethylammonium maleate, bistetraethylammonium fumarate,bistetraethylammonium citraconate, bistetraethylammonium citrate,bistetraethylammonium carbonate, tetrapropylammonium formate,tetrapropylammonium acetate, tetrapropylammonium propionate,tetrapropylammonium butanoate, tetrapropylammonium benzoate,tetrapropylammonium phthalate, tetrapropylammonium isophthalate,tetrapropylammonium terephthalate, tetrapropylammonium salicylate,tetrapropylammonium trifluoromethanesulfonate, tetrapropylammoniumtrifluoroacetate, tetrapropylammonium monochloroacetate,tetrapropylammonium dichloroacetate, tetrapropylammoniumtrichloroacetate, tetrapropylammonium hydroxide, tetrapropylammoniumnitrate, tetrapropylammonium chloride, tetrapropylammonium bromide,tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate,tetrapropylammonium oxalate, tetrapropylammonium malonate,tetrapropylammonium maleate, tetrapropylammonium fumarate,tetrapropylammonium citraconate, tetrapropylammonium citrate,tetrapropylammonium carbonate, bistetrapropylammonium oxalate,bistetrapropylammonium malonate, bistetrapropylammonium maleate,bistetrapropylammonium fumarate, bistetrapropylammonium citraconate,bistetrapropylammonium citrate, bistetrapropylammonium carbonate,tetrabutylammonium formate, tetrabutylammonium acetate,tetrabutylammonium propionate, tetrabutylammonium butanoate,tetrabutylammonium benzoate, tetrabutylammonium phthalate,tetrabutylammonium isophthalate, tetrabutylammonium terephthalate,tetrabutylammonium salicylate, tetrabutylammoniumtrifluoromethanesulfonate, tetrabutylammonium trifluoroacetate,tetrabutylammonium monochloroacetate, tetrabutylammoniumdichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammoniumhydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride,tetrabutylammonium bromide, tetrabutylammonium iodide,tetrabutylammonium methanesulfonate, tetrabutylammoniummonomethylsulfate, tetrabutylammonium oxalate, tetrabutylammoniummalonate, tetrabutylammonium maleate, tetrabutylammonium fumarate,tetrabutylammonium citraconate, tetrabutylammonium citrate,tetrabutylammonium carbonate, bistetrabutylammonium oxalate,bistetrabutylammonium malonate, bistetrabutylammonium maleate,bistetrabutylammonium fumarate, bistetrabutylammonium citraconate,bistetrabutylammonium citrate, bistetrabutylammonium carbonate,trimethylphenylammonium formate, trimethylphenylammonium acetate,trimethylphenylammonium propionate, trimethylphenylammonium butanoate,trimethylphenylammonium benzoate, trimethylphenylammonium phthalate,trimethylphenylammonium isophthalate, trimethylphenylammoniumterephthalate, trimethylphenylammonium salicylate,trimethylphenylammonium trifluoromethanesulfonate,trimethylphenylammonium trifluoroacetate, trimethylphenylammoniummonochloroacetate, trimethylphenylammonium dichloroacetate,trimethylphenylammonium trichloroacetate, trimethylphenylammoniumhydroxide, trimethylphenylammonium nitrate, trimethylphenylammoniumchloride, trimethylphenylammonium bromide, trimethylphenylammoniumiodide, trimethylphenylammonium methanesulfonate,trimethylphenylammonium monomethylsulfate, trimethylphenylammoniumoxalate, trimethylphenylammonium malonate, trimethylphenylammoniummaleate, trimethylphenylammonium fumarate, trimethylphenylammoniumcitraconate, trimethylphenylammonium citrate, trimethylphenylammoniumcarbonate, bistrimethylphenylammonium oxalate,bistrimethylphenylammonium malonate, bistrimethylphenylammonium maleate,bistrimethylphenylammonium fumarate, bistrimethylphenylammoniumcitraconate, bistrimethylphenylammonium citrate,bistrimethylphenylammonium carbonate, triethylphenylammonium formate,triethylphenylammonium acetate, triethylphenylammonium propionate,triethylphenylammonium butanoate, triethylphenylammonium benzoate,triethylphenylammonium phthalate, triethylphenylammonium isophthalate,triethylphenylammonium terephthalate, triethylphenylammonium salicylate,triethylphenylammonium trifluoromethanesulfonate, triethylphenylammoniumtrifluoroacetate, triethylphenylammonium monochloroacetate,triethylphenylammonium dichloroacetate, triethylphenylammoniumtrichloroacetate, triethylphenylammonium hydroxide,triethylphenylammonium nitrate, triethylphenylammonium chloride,triethylphenylammonium bromide, triethylphenylammonium iodide,triethylphenylammonium methanesulfonate, triethylphenylammoniummonomethylsulfate, triethylphenylammonium oxalate,triethylphenylammonium malonate, triethylphenylammonium maleate,triethylphenylammonium fumarate, triethylphenylammonium citraconate,triethylphenylammonium citrate, triethylphenylammonium carbonate,bistriethylphenylammonium oxalate, bistriethylphenylammonium malonate,bistriethylphenylammonium maleate, bistriethylphenylammonium fumarate,bistriethylphenylammonium citraconate, bistriethylphenylammoniumcitrate, bistriethylphenylammonium carbonate,benzyldimethylphenyllammonium formate, benzyldimethylphenyllammoniumacetate, benzyldimethylphenyllammonium propionate,benzyldimethylphenyllammonium butanoate, benzyldimethylphenyllammoniumbenzoate, benzyldimethylphenyllammonium phthalate,benzyldimethylphenyllammonium isophthalate,benzyldimethylphenyllammonium terephthalate,benzyldimethylphenyllammonium salicylate, benzyldimethylphenyllammoniumtrifluoromethanesulfonate, benzyldimethylphenyllammoniumtrifluoroacetate, benzyldimethylphenyllammonium monochloroacetate,benzyldimethylphenyllammonium dichloroacetate,benzyldimethylphenyllammonium trichloroacetate,benzyldimethylphenyllammonium hydroxide, benzyldimethylphenyllammoniumnitrate, benzyldimethylphenyllammonium chloride,benzyldimethylphenyllammonium bromide, benzyldimethylphenyllammoniumiodide, benzyldimethylphenyllammonium methanesulfonate,benzyldimethylphenyllammonium monomethylsulfate,benzyldimethylphenyllammonium oxalate, benzyldimethylphenyllammoniummalonate, benzyldimethylphenyllammonium maleate,benzyldimethylphenyllammonium fumarate, benzyldimethylphenyllammoniumcitraconate, benzyldimethylphenyllammonium citrate,benzyldimethylphenyllammonium carbonate,bisbenzyldimethylphenyllammonium oxalate,bisbenzyldimethylphenyllammonium malonate,bisbenzyldimethylphenyllammonium maleate,bisbenzyldimethylphenyllammonium fumarate,bisbenzyldimethylphenyllammonium citraconate,bisbenzyldimethylphenyllammonium citrate,bisbenzyldimethylphenyllammonium carbonate, and the like.

Examples of the alkaline metal salt include lithium formate, lithiumacetate, lithium propionate, lithium butanoate, lithium benzoate,lithium phthalate, lithium isophthalate, lithium terephthalate, lithiumsalicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate,lithium monochloroacetate, lithium dichloroacetate, lithiumtrichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride,lithium bromide, lithium iodide, lithium methanesulfonate, lithiumhydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate,lithium hydrogen fumarate, lithium hydrogen citraconate, lithiumhydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithiummalonate, lithium maleate, lithium fumarate, lithium citraconate,lithium citrate, lithium carbonate, sodium formate, sodium acetate,sodium propionate, sodium butanoate, sodium benzoate, sodium phthalate,sodium isophthalate, sodium terephthalate, sodium salicylate, sodiumtrifluoromethanesulfonate, sodium trifluoroacetate, sodiummonochloroacetate, sodium dichloroacetate, sodium trichloroacetate,sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide,sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodiumhydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate,sodium hydrogen citraconate, sodium hydrogen citrate, sodium hydrogencarbonate, sodium oxalate, sodium malonate, sodium maleate, sodiumfumarate, sodium citraconate, sodium citrate, sodium carbonate,potassium formate, potassium acetate, potassium propionate, potassiumbutanoate, potassium benzoate, potassium phthalate, potassiumisophthalate, potassium terephthalate, potassium salicylate, potassiumtrifluoromethanesulfonate, potassium trifluoroacetate, potassiummonochloroacetate, potassium dichloroacetate, potassiumtrichloroacetate, potassium hydroxide, potassium nitrate, potassiumchloride, potassium bromide, potassium iodide, potassiummethanesulfonate, potassium hydrogen oxalate, potassium hydrogenmalonate, potassium hydrogen maleate, potassium hydrogen fumarate,potassium hydrogen citraconate, potassium hydrogen citrate, potassiumhydrogen carbonate, potassium oxalate, potassium malonate, potassiummaleate, potassium fumarate, potassium citraconate, potassium citrate,potassium carbonate, and the like.

In the present invention, a polysiloxane (Xc-10) having a structurepartially containing one of the sulfonium salt, the iodonium salt, thephosphonium salt, and the ammonium salt may be blended as thecrosslinking catalyst (Xc) into the composition for forming asilicon-containing resist underlayer film.

As a raw material for producing (Xc-10) used here, it is possible toemploy a compound shown by the following general formula (Xm):

R^(1A) _(A1)R^(2A) _(A2)R^(3A) _(A3)Si(OR^(0A))_((4-A1-A2-A3))  (Xm)

where R^(0A) represents a hydrocarbon group having 1 to 6 carbon atoms;at least one of R^(1A), R^(2A), and R^(3A) represents an organic grouphaving the ammonium salt, the sulfonium salt, the phosphonium salt, orthe iodonium salt; the other (s) of R^(1A), R^(2A), and R^(3A) representa hydrogen atom or a monovalent organic group having 1 to 30 carbonatoms; and A1, A2, and A3 each represent 0 or 1, given that1≤A1+A2+A3≤3.

Here, examples of R^(0A) include a methyl group, an ethyl group, ann-propyl group, an iso-propyl group, an n-butyl group, an iso-butylgroup, a sec-butyl group, a tert-butyl group, an n-pentyl group, acyclopentyl group, an n-hexyl group, a cyclohexyl group, and a phenylgroup.

An example of Xm includes the following general formula (Xm-1), as ahydrolysable silicon compound having a structure partially containingthe sulfonium salt:

In the formula, R^(SA1) and R^(SA2) each represent a monovalent organicgroup such as a linear, branched, or cyclic alkyl group, alkenyl group,oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms, oran aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms; someor all of the hydrogen atoms of these groups are optionally substitutedwith an alkoxy group, an amino group, an alkylamino group, a halogenatom, or the like. Moreover, R^(SA1) and R^(SA2) may form a ringtogether with a nitrogen atom bonded to R^(SA1) and R^(SA2); when a ringis formed, R^(SA1) and R^(SA2) each represent an alkylene group having 1to 6 carbon atoms. R^(SA3) represents a divalent organic group such as alinear, branched, or cyclic alkylene group or alkenylene group having 1to 20 carbon atoms, or a substituted or unsubstituted arylene grouphaving 6 to 20 carbon atoms; some or all of hydrogen atoms of thesegroups are optionally substituted with an alkoxy group, an amino group,an alkylamino group, or the like.

Examples of X⁻ include hydroxide ion, fluoride ion, chloride ion,bromide ion, iodide ion, formate ion, acetate ion, propionate ion,butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoateion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleateion, linolenate ion, benzoate ion, p-methylbenzoate ion,p-t-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalateion, salicylate ion, trifluoroacetate ion, monochloroacetate ion,dichloroacetate ion, trichloroacetate ion, nitrate ion, chlorate ion,perchlorate ion, bromate ion, iodate ion, methanesulfonate ion,benzenesulfonate ion, toluenesulfonate ion, monomethylsulfate ion,hydrogen sulfate ion, oxalate ion, malonate ion, methylmalonate ion,ethylmalonate ion, propylmalonate ion, butylmalonate ion,dimethylmalonate ion, diethylmalonate ion, succinate ion,methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleateion, fumarate ion, citraconate ion, citrate ion, carbonate ion, and thelike.

Specific examples include the following (X⁻ is the same as above).

For example, a hydrolysable silicon compound having a structurepartially containing the iodonium salt can be shown by the followinggeneral formula (Xm-2). X is the same as above.

In the formula, R^(IA1) represents a monovalent organic group such as alinear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group,or oxoalkenyl group having 1 to 20 carbon atoms, a substituted orunsubstituted aryl group having 6 to 20 carbon atoms, or an aralkylgroup or aryloxoalkyl group having 7 to 20 carbon atoms; some or all ofthe hydrogen atoms of these groups are optionally substituted with analkoxy group, an amino group, an alkylamino group, a halogen atom, orthe like. R^(IA2) represents a divalent organic group such as a linear,branched, or cyclic alkylene group or alkenylene group having 1 to 20carbon atoms, or a substituted or unsubstituted arylene group having 6to 20 carbon atoms; some or all of the hydrogen atoms of these groupsare optionally substituted with an alkoxy group, an amino group, analkylamino group, or the like.

Specific examples include the following (X⁻ is the same as above).

For example, a hydrolysable silicon compound having a structurepartially containing the phosphonium salt can be shown by the followinggeneral formula (Xm-3). X⁻ is the same as above.

In the formula, R^(PA)1, R^(PA2), and R^(PA3) each represent a linear,branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, oroxoalkenyl group having 1 to 20 carbon atoms, a substituted orunsubstituted aryl group having 6 to 20 carbon atoms, or an aralkylgroup or aryloxoalkyl group having 7 to 20 carbon atoms; some or all ofthe hydrogen atoms of these groups are optionally substituted with analkoxy group, an amino group, an alkylamino group, a halogen atom, orthe like. Moreover, R^(PA1) and R^(PA2) may form a ring together with anitrogen atom bonded to R^(PA1) and R^(PA2); when a ring is formed,R^(PA1) and R^(PA2) each represent an alkylene group having 1 to 6carbon atoms. R^(PA4) represents a linear, branched, or cyclic alkylenegroup or alkenylene group having 1 to 20 carbon atoms, or a substitutedor unsubstituted arylene group having 6 to 20 carbon atoms; some or allof the hydrogen atoms of these groups are optionally substituted with analkoxy group, an amino group, an alkylamino group, or the like.

Specific examples include the following (X⁻ is the same as above).

For example, a hydrolysable silicon compound having a structurepartially containing the ammonium salt can be shown by the followinggeneral formula (Xm-4). X⁻ is the same as above.

In the formula, R^(NA1), R^(NA2), and R^(NA3) each represent hydrogen ora monovalent organic group such as a linear, branched, or cyclic alkylgroup, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20carbon atoms, a substituted or unsubstituted aryl group having 6 to 20carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20carbon atoms; some or all of the hydrogen atoms of these groups areoptionally substituted with an alkoxy group, an amino group, analkylamino group, or the like. Moreover, R^(NA1) and R^(NA2) may form aring together with a nitrogen atom bonded to R^(NA1) and R^(NA2); when aring is formed, R^(NA1) and R^(NA2) each represent an alkylene grouphaving 1 to 6 carbon atoms or a heterocyclic ring or heteroaromatic ringcontaining nitrogen. R^(NA4) represents a divalent organic group such asa linear, branched, or cyclic alkylene group or alkenylene group having1 to 20 carbon atoms, or a substituted or unsubstituted arylene grouphaving 6 to 20 carbon atoms; some or all of the hydrogen atoms of thesegroups are optionally substituted with an alkoxy group, an amino group,an alkylamino group, or the like. In the case where R^(NA1) and R^(NA2),or R^(NA1) and R^(NA4), form a cyclic structure which further containsunsaturated nitrogen, n^(NA3)=0; in the other cases, n^(NA3)=1.

Specific examples include the following (X is the same as above).

As a hydrolysable silicon compound simultaneously used with (Xm-1),(Xm-2), (Xm-3), and (Xm-4) to produce the crosslinking catalyst having apolysiloxane structure (Xc-10), the above-mentioned hydrolysable monomer(Sm) can be exemplified. Further, (Mm) may be added.

A reaction raw material for forming (Xc-10) can be prepared by:selecting at least one of the monomers (Xm-1), (Xm-2), (Xm-3), and(Xm-4) described above, in addition to at least one hydrolysable siliconcompound shown above, and optionally at least one (Mm); and mixing theselected materials before or during the reaction. The reactionconditions may follow the same method as the method for synthesizing thethermosetting silicon-containing material (Sx).

The molecular weight of the obtained crosslinking catalyst (Xc-10) canbe adjusted not only through the selection of the monomer but also bycontrolling the reaction conditions during polymerization. It ispreferable to use the crosslinking catalyst having a weight averagemolecular weight of 100,000 or less, more preferably 200 to 50,000,further preferably 300 to 30,000. When a crosslinking catalyst having aweight average molecular weight of 100,000 or less is used, generationof foreign matters and coating spots do not occur.

Regarding data on the weight average molecular weight, the molecularweight is expressed in terms of polystyrene which is obtained bygel-permeation chromatography (GPC) using a refractive index (RI)detector, tetrahydrofuran as an eluent, and polystyrene as a referencesubstance.

Note that one of the crosslinking catalysts (Xc-1), (Xc-2), (Xc-3),(Xc-4), and (Xc-10) can be used alone, or two or more thereof can beused in combination. The amount of the crosslinking catalyst to be addedis preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 partsby mass, based on 100 parts by mass of the base polymer (i.e., thethermosetting silicon-containing material (Sx) obtained by the abovemethod).

(Nitrogen-Containing Compound Containing Acid-Decomposable Substituent)

In the present invention, an example of a nitrogen-containing compound(Qn) containing a substituent that is decomposed by acid(acid-decomposable substituent) includes a polysiloxane made from ahydrolysable silicon compound (Qn−1) having a substituent that isdecomposed by acid at a nitrogen atom on a side chain, a hydrolysiscondensate of the compound (Qn−1) or a mixture of a compound containinga silicon compound which contains the compound (Qn−1) as a part of amonomer.

Specific examples of (Qn−1) include the following, but the compounds arenot limited to these compounds. Among these compounds, compounds havinga cyclic structure are particularly favorable.

To produce a nitrogen-containing compound (Qn) containing anacid-decomposable substituent, a raw material for forming Qn can beprepared by, for example, selecting at least one of the hydrolysablesilicon compounds (Qn−1) or (Qn−1) and at least one of the hydrolysablesilicon compounds shown above, and optionally at least one (Mm) asnecessary; and mixing the selected materials before or during thereaction. The reaction conditions may follow the same method as themethod for synthesizing the thermosetting silicon-containing material(Sx).

The molecular weight of the obtained nitrogen-containing compound (Qn)containing a substituent that can be decomposed by acid can be adjustednot only through the selection of the monomer but also by controllingthe reaction conditions during polymerization. It is preferable to usethe compound having a weight average molecular weight of 100,000 orless, more preferably 200 to 50,000, further preferably 300 to 30,000.When a compound having a weight average molecular weight of 100,000 orless is used, generation of foreign matters and coating spots do notoccur.

Regarding data on the weight average molecular weight, the molecularweight is expressed in terms of polystyrene which is obtained bygel-permeation chromatography (GPC) using a refractive index (RI)detector, tetrahydrofuran as an eluent, and polystyrene as a referencesubstance.

Note that the above-described Qn can be used alone or in combination oftwo or more thereof. The amount to be added is preferably 0.001 to 50parts by mass, more preferably 0.01 to 10 parts by mass, based on 100parts by mass of the base polymer (i.e., the thermosettingsilicon-containing material (Sx) obtained by the above method).

(Organic Acid)

To improve the stability of the inventive composition for forming asilicon-containing resist underlayer film, it is preferable to add amonovalent, divalent, or polyvalent organic acid having 1 to 30 carbonatoms. Examples of the acid added in this event include formic acid,acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoicacid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleicacid, stearic acid, linoleic acid, linolenic acid, benzoic acid,phthalic acid, isophthalic acid, terephthalic acid, salicylic acid,trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid,ethylmalonic acid, propylmalonic acid, butylmalonic acid,dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinicacid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaricacid, citraconic acid, citric acid, and the like. Particularly, oxalicacid, maleic acid, formic acid, acetic acid, propionic acid, citricacid, and the like are preferable. Moreover, a mixture of two or moreacids may be used to keep the stability. The amount of the organic acidto be added may be 0.001 to 25 parts by mass, preferably 0.01 to 15parts by mass, more preferably 0.1 to 5 parts by mass, based on 100parts by mass of silicon contained in the composition.

Otherwise, the organic acid may be blended based on the pH of thecomposition so as to satisfy preferably 0≤pH≤7, more preferably0.3≤pH≤6.5, further preferably 0.5≤pH≤6.

(Water)

In the present invention, water may be added to the composition. Whenwater is added, the polysiloxane compound in the composition ishydrated, so that the lithography performance is improved. The watercontent in the solvent component of the composition may be more than 0mass % and less than 50 mass %, particularly preferably 0.3 to 30 mass%, further preferably 0.5 to 20 mass %.

When the organic acid and the water are each added in an amount in theabove range, uniformity of the silicon-containing resist underlayer filmis not degraded, there is no risk of repelling, and there is no risk oflithography performance being lowered.

The solvent including water is used in a total amount of preferably 100to 100,000 parts by mass, particularly preferably 200 to 50,000 parts bymass, based on 100 parts by mass of the polysiloxane compound, which isthe base polymer.

(Photo-Acid Generator)

In the present invention, a photo-acid generator other than the compoundshown by the general formula (P−0) may be added to the composition. Asthe photo-acid generator used in the present invention, it is possibleto add, specifically, the materials described in paragraphs (0160) to(0179) of JP 2009-126940 A.

(Stabilizer)

Further, in the present invention, a stabilizer can be added to thecomposition. As the stabilizer, a monohydric, dihydric, or polyhydricalcohol having a cyclic ether as a substituent can be added.

Particularly, adding stabilizers shown in paragraphs (0181) to (0182) ofJP 2009-126940 A enables stability improvement of the composition forforming a silicon-containing resist underlayer film.

(Surfactant)

Further, in the present invention, a surfactant can be blended into thecomposition as necessary. Specifically, the materials described inparagraph (0185) of JP 2009-126940 A can be added as the surfactant.

(Other Components)

Further, in the present invention, a high-boiling-point solvent having aboiling point of 180° C. or more can also be added to the composition asnecessary. Examples of the high-boiling-point solvent include 1-octanol,2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol,1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol,2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol,2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol,triethylene glycol, tripropylene glycol, glycerin, gamma-butyrolactone,tripropylene glycol monomethyl ether, diacetone alcohol, n-nonylacetate, ethylene glycol monoethyl ether acetate, 1,2-diacetoxyethane,1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycolmonomethyl ether acetate, diethylene glycol monoethyl ether acetate,diethylene glycol mono-n-butyl ether acetate, propylene glycolmonomethyl ether acetate, propylene glycol monopropyl ether acetate,propylene glycol monobutyl ether acetate, dipropylene glycol monomethylether acetate, dipropylene glycol monoethyl ether acetate, and the like.

[Negative-Type Patterning Process]

(Negative-Type Patterning Process 1)

The present invention can provide a patterning process including:

forming an organic underlayer film on a body to be processed using acoating-type organic underlayer film material;

forming a silicon-containing resist underlayer film on the organicunderlayer film using the composition for forming a silicon-containingresist underlayer film described above;

forming a photoresist film on the silicon-containing resist underlayerfilm using a chemically amplified resist composition;

exposing the photoresist film to a high-energy beam or the like after aheat treatment and dissolving an unexposed portion of the photoresistfilm using an organic solvent developer to form a negative-type pattern;

transferring the pattern to the silicon-containing resist underlayerfilm by dry etching using the photoresist film having the formednegative-type pattern as a mask;

transferring the pattern to the organic underlayer film by dry etchingusing the silicon-containing resist underlayer film having thetransferred pattern as a mask; and

transferring the pattern to the body to be processed by dry etchingusing the organic underlayer film having the transferred pattern as amask (what is called “multilayer resist method”).

(Negative-Type Patterning Process 2)

Furthermore, the present invention can provide a patterning processincluding:

forming an organic hard mask mainly containing carbon on a body to beprocessed by a CVD method;

forming a silicon-containing resist underlayer film on the organic hardmask using the composition for forming a silicon-containing resistunderlayer film described above;

forming a photoresist film on the silicon-containing resist underlayerfilm using a chemically amplified resist composition;

exposing the photoresist film to a high-energy beam or the like after aheat treatment and dissolving an unexposed portion of the photoresistfilm using an organic solvent developer to form a negative-type pattern;

transferring the pattern to the silicon-containing resist underlayerfilm by dry etching using the photoresist film having the formednegative-type pattern as a mask;

transferring the pattern to the organic hard mask by dry etching usingthe silicon-containing resist underlayer film having the transferredpattern as a mask; and

transferring the pattern to the body to be processed by dry etchingusing the organic hard mask having the transferred pattern as a mask(what is called “multilayer resist method”).

When a negative-type pattern is formed using the resist underlayer filmof the present invention, the combination with the CVD film or theorganic underlayer film is optimized as described above, so that thepattern formed in the photoresist can be formed onto the substratewithout changing the size during the transfer.

Furthermore, in the photoresist film exposure, the contact angle of thepart of the silicon-containing resist underlayer film corresponding tothe exposed portion of the exposed photoresist film is preferablylowered by 10 degrees or more after the exposure than before theexposure.

When the contact angle of the exposed portion of the silicon-containingresist underlayer film is lowered by 10 degrees or more compared tobefore the exposure, difference in contact angle with the resist patternafter the negative development becomes small, adhesiveness is improved,and pattern collapse is prevented so that fine patterns can be formed.

The silicon-containing resist underlayer film used in the inventivepatterning process can be prepared on the body to be processed from theinventive composition for forming a silicon-containing resist underlayerfilm by a spin-coating method or the like as with the photoresist film.After spin-coating, the composition is preferably baked to evaporate thesolvent to promote crosslinking reaction and prevent mixing with thephotoresist film. A baking temperature in the range of 50 to 500° C. anda baking duration in the range of 10 to 300 seconds are favorably used.A particularly favorable temperature range depends on the structure ofthe device to be manufactured, but to reduce heat damage to the device,400° C. or less is preferable.

Here, as the body to be processed, a semiconductor device substrate or asemiconductor device substrate having any of a metal film, an alloyfilm, a metal carbide film, a metal oxide film, a metal nitride film, ametal oxycarbide film, and a metal oxynitride film formed as the layerto be processed (portion to be processed) or the like can be used.

As the semiconductor device substrate, a silicon substrate is generallyused, but the substrate is not particularly limited, and may have adifferent material to the layer to be processed, such as Si, amorphoussilicon (a-Si), p-Si, SiO₂, SiN, SiON, W, TiN, or Al.

As the metal of the body to be processed, any of silicon, gallium,titanium, tungsten, hafnium, zirconium, chromium, germanium, copper,silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum,iron, molybdenum, cobalt, or an alloy thereof can be used. A layer to beprocessed containing such metal includes a film of Si, SiO₂, SiN, SiON,SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, W, W—Si, Al,Cu, Al—Si, or the like, various low dielectric constant films, or anetching stopper film thereof can be used, for example. The layer cannormally be formed with a thickness of 50 to 10,000 nm, in particular,100 to 5,000 nm.

In the negative-type patterning process of the present invention, thephotoresist film can be a chemically amplified type, and is notparticularly limited as long as a negative-type pattern can be formed bya development with an organic solvent developer.

For example, when the exposure process in the present invention is anexposure process by ArF excimer laser beam, any resist composition for anormal ArF excimer laser beam can be used to form the photoresist film.

Many candidates for such a resist composition for an ArF excimer laserbeam are already known, and the known resins are broadly divided intopoly(meth)acrylic types, COMA (Cyclo Olefin Maleic Anhydride) types,COMA-(meth)acryl hybrid types, ROMP (Ring Opening MethathesisPolymerization) types, polynorbornene types, and the like. Inparticular, a resist composition containing a poly(meth)acrylic resinensures etching resistance by introducing an alicyclic skeleton to aside chain, and therefore, resolution performance is more excellent thanother types of resins.

In the negative-type patterning process, a silicon-containing resistunderlayer film is formed, then a photoresist film is formed thereonwith a photoresist composition solution, and as with thesilicon-containing resist underlayer film the spin-coating method isfavorably used. After spin-coating the photoresist composition, thecomposition is prebaked, and a temperature in the range of 80 to 180° C.and a duration in the range of 10 to 300 seconds are preferable.Subsequently, exposure is performed, and organic solvent development isperformed to obtain a negative-type resist pattern. In addition, apost-exposure bake (PEB) is preferably performed after the exposure.

As the organic solvent developer, a developer containing one or moresolvents selected from 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone,4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butylacetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamylacetate, phenyl acetate, propyl formate, butyl formate, isobutylformate, amyl formate, isoamyl formate, methyl valerate, methylpentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyllactate, propyl lactate, butyl lactate, isobuthyl lactate, amyl lactate,isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate,benzyl acetate, methyl phenylacetate, benzyl formate, phenylethylformate, methyl 3-phenylpropionate, benzyl propionate, ethylphenylacetate, and 2-phenylethyl acetate as a component can be used. Adeveloper having one type of developer component or a total of two ormore types in an amount of 50 mass % or more is preferablly used fromthe viewpoint of improving pattern collapse or the like.

When using a silicon-containing resist underlayer film as an etchingmask in the inventive patterning process, the etching can be performedusing a gas mainly containing a fluorine-containing gas such as afluorocarbon-based gas. To reduce film loss of the photoresist film, thesilicon-containing resist underlayer film preferably has a high etchingspeed to the gas.

When an organic underlayer film is provided between thesilicon-containing resist underlayer film and the body to be processedand the organic underlayer film is used as an etching mask of the bodyto be processed in such a multilayer resist method, the organicunderlayer film is preferably an organic film having an aromaticskeleton, but when the organic underlayer film is a sacrificial film orthe like, the organic underlayer film may be a silicon-containingorganic underlayer film as long as the silicon content is 15 mass % orless.

As such an organic underlayer film, a known organic underlayer film fora 3-layer resist method, an organic underlayer film known as anunderlayer film for a 2-layer resist method using a silicon resistcomposition, a 4,4′-(9-fluorenylidene)bisphenol novolak resin (molecularweight 11,000) disclosed in JP 2005-128509 A, or various resinsincluding novolak resins such as those known as resist underlayer filmmaterials for a 2-layer resist method or a 3-layer resist method can beused. In addition, when a higher heat resistance than a normal novolakresin is desired, a polycyclic skeleton such as a6,6′-(9-fluorenylidene)-di(2-naphthol)novolak resin can be introduced,and a polyimide resin may further be selected (see, for example, JP2004-153125 A).

The organic underlayer film can be formed on the body to be processedusing a composition solution by a spin-coating method or the like aswith the photoresist composition. After forming the organic underlayerfilm by a spin-coating method or the like, the composition is preferablybaked to evaporate the organic solvent. A baking temperature in therange of 80 to 300° C. and a baking duration in the range of 10 to 300seconds are favorably used.

Note that the organic underlayer film preferably has a thickness of 5 nmor more, in particular, 20 nm or more, and 50,000 nm or less, and thesilicon-containing resist underlayer film according to the presentinvention preferably has a thickness of 1 nm or more and 500 nm or less,more preferably 300 nm or less, and further preferably 200 nm or less,although the thicknesses are not particularly limited and vary dependingon etching conditions. In addition, the photoresist film preferably hasa thickness of 1 nm or more and 200 nm or less.

[Inventive Patterning Process by 3-Layer Resist Method]

The negative-type patterning process of the present invention by a3-layer resist method as described above is as follows (see FIG. 1 ). Inthis process, firstly, an organic underlayer film 2 is prepared on abody to be processed 1 by spin-coating (FIG. 1 (I-A)). This organicunderlayer film 2 preferably has a high etching resistance since theorganic underlayer film 2 acts as a mask when etching the body to beprocessed 1, and the organic underlayer film 2 is preferably crosslinkedby heat or acid after being formed by spin-coating since the organicunderlayer film 2 is required not to mix with a silicon-containingresist underlayer film 3 to be formed thereon.

Then, the silicon-containing resist underlayer film 3 is formed thereonby spin-coating using the inventive composition for forming asilicon-containing resist underlayer film (FIG. 1 (I-B)), and aphotoresist film 4 is formed thereon by spin-coating (FIG. 1 (I-C)).Note that the silicon-containing resist underlayer film 3 can be formedusing a composition such that when the photoresist film 4 is exposed,the silicon-containing resist underlayer film 3 corresponding to theexposed portion has a contact angle with pure water of 40 degrees ormore and less than 70 degrees after the exposure.

Using a mask 5, the photoresist film 4 is subjected to a usual patternexposure using a light source P appropriate for the photoresist film 4,for example, KrF excimer laser beam, ArF excimer laser beam, F₂ laserbeam, or EUV beam. A pattern can be formed preferably by any of aphotolithography with a wavelength of 10 nm or more and 300 nm or less,direct drawing with electron beam, and nanoimprinting, or a combinationthereof (FIG. 1 (I-D)). Thereafter, heat treatment is performed under acondition matching with the photoresist film (FIG. 1 (I-E)). After that,development (negative development) with an organic developer and then,if necessary, rinsing are performed, so that a negative-type resistpattern 4a can be obtained (FIG. 1 (I-F)). Note that in FIG. 1 (I-D), 4′is a portion of photoresist film 4 that was changed by the patternexposure.

Next, using this negative-type resist pattern 4a as an etching mask, dryetching is performed, for example, with fluorine-based gas plasma, undera dry etching condition where the etching speed of thesilicon-containing resist underlayer film 3 is significantly highrelative to the photoresist film 4. As a result, a negative-typesilicon-containing resist underlayer film pattern 3a can be obtainedwith little influence from pattern change due to the side etching of thephotoresist film (FIG. 1 (I-G)).

Next, the organic underlayer film 2 is dry-etched under a dry etchingcondition where the etching speed of the organic underlayer film 2 issignificantly high relative to the substrate having the negative-typesilicon-containing resist underlayer film pattern 3a obtained bytransferring the negative-type resist pattern 4a. The dry etching maybe, for example, reactive dry etching with gas plasma containing oxygen,or reactive dry etching with gas plasma containing hydrogen andnitrogen. By this etching, a negative-type organic underlayer filmpattern 2a is obtained, and the uppermost photoresist film is usuallylost at the same time (FIG. 1 (I-H)). Then, using the negative-typeorganic underlayer film pattern 2a thus obtained as an etching mask, thebody to be processed 1 is dry-etched, for example, by employingfluorine-based dry etching or chlorine-based dry etching. In this way,the body to be processed 1 can be etched precisely, thereby transferringa negative-type pattern 1a to the body to be processed 1 (FIG. 1 (I-I)).

Furthermore, in the patterning process by the 3-layer resist method,when the photoresist film 4 is exposed to form a pattern, not only thephotoresist film 4 but also the silicon-containing resist underlayerfilm 3 formed underneath is also sometimes changed. Hereinafter, thiswill be described with reference to FIG. 2 . Note that description willbe omitted where it is the same as above.

A pattern is formed in the photoresist film 4 by a pattern exposureusing the mask 5 (FIG. 2 (II-D)). Next, a heat treatment is performed,and for example, when a thermosetting silicon-containing material (Sx)contained in the silicon-containing resist underlayer film 3 has aprotecting group, the protecting group of the thermosettingsilicon-containing material contained in the silicon-containing resistunderlayer film 3 formed underneath the photoresist film 4 is eliminatedby the action of acid that is generated in the exposed portion of thephotoresist film 4, and a hydrophilic group (hydroxy group, carboxygroup, or the like) is generated. As a result, a portion 3′ where thesilicon-containing resist underlayer film 3 changed is formed underneaththe portion 4′ where the photoresist film 4 changed after the exposure(FIG. 2 (II-E)). The contact angle of this changed portion 3′ to purewater becomes lower than the contact angle of the silicon-containingresist underlayer film 3 by the elimination of the protecting group(that is, the generation of the hydrophilic group). By using thischange, the contact angle to pure water of the portion 3′ of thesilicon-containing resist underlayer film 3 that changed after theexposure corresponding to the exposed portion of the photoresist film 4when the photoresist film 4 is exposed, can be set to 40 degrees or moreand less than 70 degrees even when the contact angle of thesilicon-containing resist underlayer film 3 itself is high.

The subsequent process can be performed as described above (FIG. 2(II-F) to (II-I)).

In this manner, the contact angle of the changed portion 3′ of thesilicon-containing resist underlayer film 3 can be adjusted by thepresence or absence of a protecting group of the thermosettingsilicon-containing material contained in the silicon-containing resistunderlayer film 3. In this way, the degree of freedom of the componentof the composition for forming a silicon-containing resist underlayerfilm that can be used is raise, and in addition, the degree of freedomin development means can also be raised.

Note that, although a case where the thermosetting silicon-containingmaterial has a protecting group that is removed by acid is describedabove, the protecting group can also be removed by the heat at the timeof the exposure, there can be a change other than the removal of aprotecting group, and there are no particular limitations. In addition,the mode of the change in the silicon-containing resist underlayer film3 after exposure and patterning is also not particularly limited.

Furthermore, in the above-described process according to the 3-layerresist method, an organic hard mask formed by a CVD method is alsoapplicable in place of the organic underlayer film 2. In this case also,the body to be processed can be processed by the same procedure asdescribed above.

The inventive composition for forming a silicon-containing resistunderlayer film makes it possible to form an upper layer resist patternwith favorable LWR and CDU, and also to form a semiconductor-devicepattern on a substrate with high yield because of excellent dry etchingselectivity relative to an upper layer resist and an underlayer organicfilm or an organic hard mask such as a CVD carbon film.

EXAMPLE

Hereinafter, the present invention will be specifically described withreference to Synthesis Examples, Examples, and Comparative Examples.However, the present invention is not limited to these descriptions.Note that, in the following examples, % means mass %, and the molecularweight measurement was carried out by GPC.

Synthesis of Silicon-Containing Polymer

Synthesis Example 1

To a mixture containing 200 g of methanol, 0.1 g of methanesulfonic acidand 60 g of deionized water, a mixture containing 17.0 g of Monomer 101,53.3 g of Monomer 102, and 7.5 g of Monomer 130 was added and maintainedat 40° C. for 12 hours to perform hydrolysis condensation. Aftercompletion of the reaction, 200 g of propylene glycol ethyl ether (PGEE)was added thereto. Then, by-produced alcohol was distilled off underreduced pressure. 1000 ml of ethyl acetate and 280 g of PGEE were addedthereto and the resulting water layer was separated. Into the remainingorganic layer, 100 ml of ion-exchanged water was added; and theresulting mixture was stirred, settled, and separated into the layers.This procedure was repeated three times. The remaining organic layer wasconcentrated under reduced pressure to obtain 480 g of the PGEE solutionof the silicon-containing compound 1 (compound concentration of 10%).The molecular weight thereof was measured in terms of polystyrene andfound Mw=2,400.

Synthesis Example 2 to Synthesis Example 55 were carried out under thesame conditions as in Synthesis Example 1 by using the monomers(reaction raw materials for silicon-containing polymers) shown in Tables1-1 and 1-2 to obtain the target products.

Synthesis Example 56

To a mixture containing 200 g of methanol, 0.1 g of 35% hydrochloricacid, and 60 g of deionized water, a mixture containing 6.8 g of Monomer101, 60.9 g of Monomer 102, and 20.1 g of Monomer 149 was added andmaintained at 40° C. for 12 hours to perform hydrolysis condensation.After completion of the reaction, 620 g of propylene glycol ethyl ether(PGEE) was added thereto. Then, by-produced alcohol was distilled offunder reduced pressure to obtain 570 g of the PGEE solution of thesilicon-containing compound 20 (compound concentration of 10%). Themolecular weight thereof was measured in terms of polystyrene and foundMw=2,100.

Synthesis Example 57 to Synthesis Example 60 were carried out under thesame conditions as in Synthesis Example 56 by using the monomers shownin Table 1-2 to obtain the target products.

TABLE 1-1 Synthesis Example Reaction Raw Material Mw 1 Monomer 101: 17.0g, Monomer 102: 53.3 g, Monomer 130: 7.5 g 2400 2 Monomer 100: 5.0 g,Monomer 101: 13.6 g, Monomer 102: 53.3 g, 2700 Monomer 131: 7.6 g 3Monomer 100: 5.0 g, Monomer 101: 13.6 g, Monomer 102: 53.3 g, 2700Monomer 132: 7.9 g 4 Monomer 100: 5.0 g, Monomer 101: 13.6 g, Monomer102: 53.3 g, 2200 Monomer 133: 6.5 g 5 Monomer 100: 5.0 g, Monomer 101:13.6 g, Monomer 102: 53.3 g, 2600 Monomer 134: 6.9 g 6 Monomer 101: 17.0g, Monomer 102: 53.3 g, Monomer 135: 6.4 g 2700 7 Monomer 100: 5.0 g,Monomer 101: 13.6 g, Monomer 102: 53.3 g, 2600 Monomer 136: 6.8 g 8Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 137: 15.7 g 2400 9Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 138: 13.1 g 2600 10Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 139: 14.8 g 2500 11Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 140: 13.9 g 2400 12Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 141: 10.4 g 2700 13Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 142: 20.8 g 2200 14Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 143: 19.1 g 2400 15Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 144: 9.0 g 2300 16Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 145: 13.2 g 2300 17Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 146: 12.7 g 2800 18Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 147: 13.3 g 2900 19Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 148: 12.1 g 2800 20Monomer 101: 17.0 g, Monomer 102: 45.7 g, Monomer 154: 21.6 g 2800 21Monomer 101: 17.0 g, Monomer 102: 45.7 g, Monomer 155: 20.3 g 2800 22Monomer 101: 17.0 g, Monomer 102: 45.7 g, Monomer 156: 20.3 g 2300 23Monomer 101: 17.0 g, Monomer 102: 45.7 g, Monomer 157: 23.4 g 2700 24Monomer 101: 17.0 g, Monomer 102: 45.7 g, Monomer 158: 23.6 g 2200 25Monomer 101: 20.4 g, Monomer 102: 38.1 g, Monomer 159: 27 g 2700 26Monomer 101: 20.4 g, Monomer 102: 38.1 g, Monomer 160: 34.3 g 2200 27Monomer 101: 20.4 g, Monomer 102: 38.1 g, Monomer 161: 26.7 g, 2000Monomer 170: 8.4 g 28 Monomer 101: 20.4 g, Monomer 102: 38.1 g, Monomer162: 19.1 g, 2300 Monomer 170: 8.4 g 29 Monomer 101: 20.4 g, Monomer102: 38.1 g, Monomer 163: 20.0 g, 2400 Monomer 170: 8.4 g 30 Monomer101: 13.6 g, Monomer 102: 53.3 g, Monomer 140: 7.0 g, 2800 Monomer 111:7.0 g 31 Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 130: 7.5 g,2300 Monomer 111: 7.0 g 32 Monomer 101: 13.6 g, Monomer 102: 53.3 g,Monomer 140: 7.0 g, 2200 Monomer 114: 6.2 g 33 Monomer 101: 13.6 g,Monomer 102: 53.3 g, Monomer 144: 4.5 g, 2300 Monomer 111: 7.0 g 34Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer 151: 6.6 g, 2400Monomer 116: 8.9 g 35 Monomer 101: 13.6 g, Monomer 102: 53.3 g, Monomer134: 6.9 g, 2600 Monomer 114: 6.2 g 36 Monomer 101: 10.2 g, Monomer 102:53.3 g, Monomer 133: 13.0 g, 2200 Monomer 115: 5.1 g 37 Monomer 101:10.2 g, Monomer 102: 53.3 g, Monomer 138: 13.1 g, 2200 Monomer 113: 7.3g 38 Monomer 101: 10.2 g, Monomer 102: 53.3 g, Monomer 139: 14.8 g, 2500Monomer 113: 7.3 g 39 Monomer 101: 10.2 g, Monomer 102: 53.3 g, Monomer159: 13.5 g, 2400 Monomer 113: 7.3 g 40 Monomer 101: 10.2 g, Monomer102: 53.3 g, Monomer 157: 15.6 g, 2600 Monomer 110: 5.9 g 41 Monomer101: 10.2 g, Monomer 102: 53.3 g, Monomer 146: 12.7 g, 3000 Monomer 110:5.9 g 42 Monomer 101: 10.2 g, Monomer 102: 53.3 g, Monomer 144: 9.0 g,2800 Monomer 113: 7.3 g 43 Monomer 101: 10.2 g, Monomer 102: 53.3 g,Monomer 158: 15.7 g, 2000 Monomer 111: 7.0 g 44 Monomer 101: 10.2 g,Monomer 102: 53.3 g, Monomer 144: 9.0 g, 2900 Monomer 110: 5.9 g

TABLE 1-2 Synthesis Example Reaction Raw Material Mw 45 Monomer 101:10.2 g, Monomer 102: 53.3 g, 2600 Monomer 158: 15.7 g, Monomer 116: 8.9g 46 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2000 Monomer 135: 19.2 g,Monomer 112: 6.6 g 47 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2300Monomer 146: 19.1 g, Monomer 116: 8.9 g 48 Monomer 101: 6.8 g, Monomer102: 53.3 g, 2500 Monomer 143: 28.7 g, Monomer 112: 6.6 g 49 Monomer101: 6.8 g, Monomer 102: 53.3 g, 2100 Monomer 133: 19.5 g, Monomer 110:5.9 g 50 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2500 Monomer 150: 19.4g, Monomer 111: 7.0 g 51 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2900Monomer 150: 19.4 g, Monomer 116: 8.9 g 52 Monomer 101: 6.8 g, Monomer102: 53.3 g, 2400 Monomer 133: 19.5 g, Monomer 114: 6.2 g 53 Monomer101: 6.8 g, Monomer 102: 53.3 g, 2500 Monomer 147: 20.0 g, Monomer 111:7.0 g 54 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2700 Monomer 143: 28.7g, Monomer 111: 7.0 g 55 Monomer 101: 6.8 g, Monomer 102: 53.3 g, 2800Monomer 146: 19.1 g, Monomer 111: 7.0 g 56 Monomer 101: 6.8 g, Monomer102: 60.9 g, 2100 Monomer 149: 20.1 g 57 Monomer 101: 6.8 g, Monomer102: 60.9 g, 2500 Monomer 150: 12.9 g 58 Monomer 101: 6.8 g, Monomer102: 60.9 g, 2000 Monomer 151: 13.2 g 59 Monomer 101: 6.8 g, Monomer102: 60.9 g, 2200 Monomer 152: 15.9 g 60 Monomer 101: 6.8 g, Monomer102: 60.9 g, 2000 Monomer 153: 14.7 g

Synthesis of Silicon-Containing Curing Catalyst

[Synthesis Example 2-1]

To a mixture containing 120 g of methanol, 0.1 g of 70% nitric acid, and60 g of deionized water, a mixture containing 13.6 g of Monomer 101,53.3 g of Monomer 102, and 12.9 g of Monomer 121 was added and stirredfor 20 hours at room temperature. 500 g of PGEE was added to theobtained reaction mixture and by-produced alcohol and excessive waterwere distilled off under reduced pressure to obtain 450 g of the PGEEsolution of the polysiloxane compound Z−1 (polymer concentration of10%). The molecular weight thereof was measured in terms of polystyreneand found Mw=3,000.

Examples and Comparative Examples

Silicon-Containing Compounds 1 to 60 obtained in the Synthesis Example,heat-curing catalysts, additives, photo-acid generators shown in Table 3(compounds shown by the general formula (P−0) or the like), solvents,and water were mixed at ratios shown in Tables 2-1 to 2-4. Each mixturewas filtered through a 0.1 μm filter made of fluorinated resin. Thus,composition solutions for forming a silicon-containing resist underlayerfilm were prepared and referred to as Sol. 1 to 77.

TABLE 2-1 Silicon- Heat-curing Photo-acid containing catalyst Additivegenerator Solvent Sol. compound (parts by (parts by (parts by (parts byWater No . (parts by mass) mass) mass) mass) mass) (parts by mass) 1  1TPSNO₃ Maleic acid PAG-1 PGEE Water (1.0) (0.01) (0.01) (0.01) (150)(15) 2  2 TPSNO₃ Maleic acid PAG-6 PGEE Water (1.0) (0.01) (0.01) (0.01)(150) (15) 3  3 TPSNO₃ Maleic acid PAG-7 PGEE Water (1.0) (0.01) (0.01)(0.01) (150) (15) 4  4 TPSNO₃ Maleic acid PAG-8 PGEE Water (1.0) (0.01)(0.01) (0.01) (150) (15) 5  5 TPSNO₃ Maleic acid PAG-9 PGEE Water (1.0)(0.01) (0.01) (0.01) (150) (15) 6  6 TPSNO₃ Maleic acid PAG-10 PGEEWater (1.0) (0.01) (0.01) (0.01) (150) (15) 7  7 TPSNO₃ Maleic acidPAG-11 PGEE Water (1.0) (0.01) (0.01) (0.01) (150) (15) 8  1 QBANO₃Maleic acid PAG-12 PGEE Water (1.0) (0.01) (0.01) (0.01) (150) (15) 9  2QBANO₃ Maleic acid PAG-12 PGEE Water (1.0) (0.01) (0.01) (0.01) (150)(15) 10  3 QBANO₃ Maleic acid PAG-1 PGEE Water (1.0) (0.01) (0.01)(0.01) (150) (15) 11  4 QBANO₃ Maleic acid PAG-2 PGEE Water (1.0) (0.01)(0.01) (0.01) (150) (15) 12  5 QBANO₃ Maleic acid PAG-3 PGEE Water (1.0)(0.01) (0.01) (0.01) (150) (15) 13  6 QBANO₃ Maleic acid PAG-4 PGEEWater (1.0) (0.01) (0.01) (0.01) (150) (15) 14  7 QBANO₃ Maleic acidPAG-5 PGEE Water (1.0) (0.01) (0.01) (0.01) (150) (15) 15  1 QBANO3Maleic acid PAG-13 PGEE Water (1.0) (0.01) (0.01) (0.01) (150) (15) 16 1 TPSMA Maleic acid PAG-14 PGEE Water (1.0) (0.01) (0.01) (0.01) (150)(15) 17  1 TPSNO₃ Maleic acid PAG-15 PGEE Water (1.0) (0.01) (0.01)(0.01) (150) (15) 18  8 TPSNO₃ Maleic acid PAG-12 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 19  9 TPSNO₃ Maleic acid PAG-1 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 20 10 TPSNO₃ Maleic acidPAG-2 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 21 11 TPSNO₃Maleic acid PAG-3 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 22 12TPSNO₃ Maleic acid PAG-4 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 23 13 TPSNO₃ Maleic acid PAG-5 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 24 14 TPSNO₃ Maleic acid PAG-6 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 25 15 TPSNO₃ Maleic acid PAG-7 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45)

TABLE 2-2 Silicon- Heat-curing Photo-acid containing catalyst Additivegenerator Solvent Sol. compound (parts by (parts by (parts by (parts byWater No . (parts by mass) mass) mass) mass) mass) (parts by mass) 26 16TPSNO₃ Maleic acid PAG-8 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 27 17 TPSNO₃ Maleic acid PAG-9 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 28 18 TPSNO₃ Maleic acid PAG-10 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 29 19 TPSNO₃ Maleic acid PAG-11 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 30 20 TPSNO₃ Maleic acidPAG-12 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 31 21 TPSMAMaleic acid PAG-2 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 32 21QBANO₃ Maleic acid PAG-3 PGEE Water (1.0) (0.04) (0.01) (0.01) (450)(45) 33 21 TPSTFA Maleic acid PAG-4 PGEE Water (1.0) (0.04) (0.01)(0.01) (450) (45) 34 21 QMAMA Maleic acid PAG-5 PGEE Water (1.0) (0.04)(0.01) (0.01) (450) (45) 35 21 TPSNO₃ Maleic acid PAG-1 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 36 22 TPSNO₃ Maleic acid PAG-2 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 37 23 TPSNO₃ Maleic acidPAG-3 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 38 24 TPSNO₃Maleic acid PAG-4 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 39 25TPSNO₃ Maleic acid PAG-5 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 40 26 TPSNO₃ Maleic acid PAG-6 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 41 27 TPSNO₃ Maleic acid PAG-7 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 42 28 TPSNO₃ Maleic acid PAG-8 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 43 29 TMPANO₃ Maleic acid PAG-9 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 44 30 TMPANO₃ Maleic acidPAG-10 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 45 31 QBANO₃Maleic acid PAG-6 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 46 32QBANO₃ Maleic acid PAG-7 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 47 33 QBANO₃ Maleic acid PAG-8 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 48 34 QBANO₃ Maleic acid PAG-9 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 49 35 QBANO₃ Maleic acid PAG-10 PGEE Water(1.0) (0.01) (0.01) (0.01) (450) (45) 50 36 QBANO₃ Maleic acid PAG-11PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45)

TABLE 2-3 Silicon- Heat-curing Photo-acid containing catalyst Additivegenerator Solvent Sol. compound (parts by (parts by (parts by (parts byWater No . (parts by mass) mass) mass) mass ) mass) (parts by mass) 5137 QBANO₃ Maleic acid PAG-12 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 52 38 QBANO₃ Maleic acid PAG-1 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 53 39 QBANO₃ Maleic acid PAG-2 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 54 40 QBANO₃ Maleic acid PAG-3 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 5 5 41 QBANO₃ Maleic acid PAG-4 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 5 6 42 QBANO₃ Maleic acidPAG-5 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 57 43 QBANO₃Maleic acid PAG-6 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 58 44QBANO₃ Maleic acid PAG-7 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 59 45 QBANO₃ Maleic acid PAG-8 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 60 46 QBANO₃ Maleic acid PAG-9 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 61 47 QBANO₃ Maleic acid PAG-10 PGEE Water(1.0) (0.01) (0.01) (0.01) (450) (45) 62 48 QBANO₃ Maleic acid PAG-11PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 63 49 QBANO₃ Maleicacid PAG-12 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 64 50QBANO₃ Maleic acid PAG-1 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 6 5 51 QBANO₃ Maleic acid PAG-2 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 66 52 QBANO₃ Maleic acid PAG-3 PGEE Water (1.0) (0.01)(0.01) (0.01) (450) (45) 67 53 QBANO₃ Maleic acid PAG-4 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 68 54 QBANO₃ Maleic acid PAG-5 PGEEWater (1.0) (0.01) (0.01) (0.01) (450) (45) 69 5 5 QBANO₃ Maleic acidPAG-6 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 70 5 6 QBANO₃Maleic acid PAG-7 PGEE Water (1.0) (0.01) (0.01) (0.01) (450) (45) 71 57QBANO₃ Maleic acid PAG-8 PGEE Water (1.0) (0.01) (0.01) (0.01) (450)(45) 72 58 QBANO₃ Maleic acid PAG-9 PGEE Water (1.0) (0.01) (0.01)(0.01) (450) (45) 73 59 QBANO₃ Maleic acid PAG-10 PGEE Water (1.0)(0.01) (0.01) (0.01) (450) (45) 74 60 Z-1 Maleic acid PAG-11 PGEE Water(1.0) (0.01) (0.01) (0.01) (450) (45)

TABLE 2-4 Silicon- Heat- Photo- containing curing acid Solvent Watercompound catalyst Additive generator (parts (parts Sol. (parts by (parts(parts (parts by by by No. mass) by mass) by mass) mass) mass) mass) 7519 QBANO₃ Maleic PAG-13 PGEE Water (1.0) (0.01) acid (0.01) (450) (45)(0.01) 76 19 TPSMA Maleic PAG-14 PGEE Water (1.0) (0.01) acid (0.01)(450) (45) (0.01) 77 19 TPSNO₃ Maleic PAG-15 PGEE Water (1.0) (0.01)acid (0.01) (450) (45) (0.01)TPSNO₃ triphenylsulfonium nitrateTMPANO₃: trimethylphenylammonium nitrateTPSMA mono(triphenylsulfonium)maleateQBANO₃ tetrabutylammonium nitrateTPSTFA triphenylsulfonium trifluoroacetateQMAMA mono (tetramethylammonium)maleatePGEE propylene glycol ethyl ether

TABLE 3 PAG 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Patterning Test by ArF Exposure and Negative-Type Development

A spin-on carbon film ODL-301 (carbon content of 88 mass %) availablefrom Shin-Etsu Chemical Co., Ltd., was formed with a thickness of 200 nmon a silicon wafer. The composition for forming a silicon-containingresist underlayer film Sols. 1 to 17 were applied thereon and heated at240° C. for 60 seconds to prepare silicon-containing films: Film 1 to 17having a film thickness of 35 nm.

Subsequently, an ArF resist solution for negative development shown inTable 4 (PR-A1 and PR-A2) was applied onto the silicon-containing filmand baked at 100° C. for 60 seconds to form a photoresist layer with athickness of 100 nm. A liquid immersion top coat (TC-1) was applied ontothe photoresist film and baked at 90° C. for 60 seconds to form a topcoat with a thickness of 50 nm.

An ArF resist solution for negative development shown in Table 4 (PR-A3)was separately applied onto the silicon-containing film and baked at100° C. for 60 seconds to form a photoresist layer with a thickness of100 nm.

Subsequently, this was exposed with an ArF liquid immersion exposureapparatus (NSR-S610C manufactured by Nikon Corporation, NA: 1.30, σ:0.98/0.65, 35° polarized dipole illumination, 6% halftone phase shiftmask), followed by baking (PEB) at 100° C. for 60 seconds. With rotatingat 30 rpm, a developer of butyl acetate was discharged from a developernozzle for 3 seconds. Then the rotation was stopped to performpuddle-development for 27 seconds, spin-drying was performed afterrinsing with diisoamyl ether, and baking was performed at 100° C. for 20seconds to evaporate the rinse solvent.

By this patterning, a negative-type line-and-space pattern of 43 nm wasobtained. The cross-sectional profile of the obtained pattern wasmeasured by an electron microscope (S−4700) manufactured by Hitachi,Ltd. and the pattern roughness (LWR) was measured by an electronmicroscope (CG4000) manufactured by Hitachi High-Technologies Corp.(Tables 6-1 and 6-2).

TABLE 4 Water- Acid repellent Polymer generator Base polymer Solvent(parts (parts by (parts by (parts by (parts PR by mass) mass) mass)mass) by mass) PR-A1 PRP-A1 PAG1 Quencher None PGMEA (100) (7.0) (1.0)(2,500) PR-A2 PRP-A2 PAG1 Quencher None PGMEA (100) (7.0) (1.0) (2,500)PR-A3 PRP-A2 PAG1 Quencher Water- PGMEA (100) (10.0) (2.0) repellent(2,500) polymer 1 (4.0)Polymer for a resist: PRP-A1

-   -   Molecular weight (Mw)=8,600    -   Dispersity (Mw/Mn)=1.88

Polymer for a resist: PRP-A2

-   -   Molecular weight (Mw)=8,900    -   Dispersity (Mw/Mn)=1.93

Acid generator: PAG 1 (shown in Table 4)

Base: Quencher

The liquid immersion top coat (TC-1) was prepared by dissolving a resinof the composition shown in Table 5 in a solvent and filtering through a0.1 μm filter made of fluorinated resin.

Top coat polymer

-   -   Molecular weight (Mw)=8,800    -   Dispersity (Mw/Mn)=1.69

TABLE 5 Polymer Organic solvent (parts by mass) (parts by mass) TC-1 Topcoat polymer Diisoamyl ether (2700) (100) 2-methyl-1-butanol (270)

TABLE 6-1 Silicon- containing Pattern resist sectional underlayer ArFprofile after Example film resist development LWR Example 1-1 Film 1PR-A1 Vertical profile 1.6 Example 1-2 Film 2 PR-A1 Vertical profile 1.7Example 1-3 Film 3 PR-A1 Vertical profile 1.6 Example 1-4 Film 4 PR-A1Vertical profile 1.7 Example 1-5 Film 5 PR-A1 Vertical profile 1.6Example 1-6 Film 6 PR-A1 Vertical profile 1.6 Example 1-7 Film 7 PR-A1Vertical profile 1.6 Example 1-8 Film 8 PR-A1 Vertical profile 1.6Example 1-9 Film 9 PR-A1 Vertical profile 1.6 Example 1-10 Film 10 PR-A1Vertical profile 1.7 Example 1-11 Film 11 PR-A1 Vertical profile 1.6Example 1-12 Film 12 PR-A1 Vertical profile 1.6 Example 1-13 Film 13PR-A1 Vertical profile 1.7 Example 1-14 Film 14 PR-A1 Vertical profile1.7 Example 1-15 Film 1 PR-A2 Vertical profile 1.6 Example 1-16 Film 2PR-A2 Vertical profile 1.6 Example 1-17 Film 3 PR-A2 Vertical profile1.7 Example 1-18 Film 4 PR-A2 Vertical profile 1.6 Example 1-19 Film 5PR-A2 Vertical profile 1.7 Example 1-20 Film 6 PR-A2 Vertical profile1.6 Example 1-21 Film 7 PR-A2 Vertical profile 1.6 Example 1-22 Film 8PR-A2 Vertical profile 1.6 Example 1-23 Film 9 PR-A2 Vertical profile1.6 Example 1-24 Film 10 PR-A2 Vertical profile 1.6 Example 1-25 Film 11PR-A2 Vertical profile 1.7 Example 1-26 Film 12 PR-A2 Vertical profile1.7 Example 1-27 Film 13 PR-A2 Vertical profile 1.6 Example 1-28 Film 14PR-A2 Vertical profile 1.6 Example 1-29 Film 1 PR-A3 Vertical profile1.6 Example 1-30 Film 2 PR-A3 Vertical profile 1.6 Example 1-31 Film 3PR-A3 Vertical profile 1.7 Example 1-32 Film 4 PR-A3 Vertical profile1.7 Example 1-33 Film 5 PR-A3 Vertical profile 1.6 Example 1-34 Film 6PR-A3 Vertical profile 1.6 Example 1-35 Film 7 PR-A3 Vertical profile1.6 Example 1-36 Film 8 PR-A3 Vertical profile 1.6 Example 1-37 Film 9PR-A3 Vertical profile 1.6 Example 1-38 Film 10 PR-A3 Vertical profile1.6 Example 1-39 Film 11 PR-A3 Vertical profile 1.6 Example 1-40 Film 12PR-A3 Vertical profile 1.7 Example 1-41 Film 13 PR-A3 Vertical profile1.6 Example 1-42 Film 14 PR-A3 Vertical profile 1.6

TABLE 6-2 Silicon- containing Pattern resist sectional underlayer ArFprofile after Example film resist development LWR Comparative Film 15PR-A1 Vertical profile 1.9 Example 1-1 Comparative Film 16 PR-A1Vertical profile 2.2 Example 1-2 Comparative Film 17 PR-A1 Verticalprofile 2.1 Example 1-3 Comparative Film 15 PR-A2 Vertical profile 1.9Example 1-4 Comparative Film 16 PR-A2 Vertical profile 2.0 Example 1-5Comparative Film 17 PR-A2 Vertical profile 2.0 Example 1-6 ComparativeFilm 15 PR-A3 Vertical profile 2.0 Example 1-7 Comparative Film 16 PR-A3Vertical profile 2.0 Example 1-8 Comparative Film 17 PR-A3 Verticalprofile 2.1 Example 1-9

As shown in Tables 6-1 and 6-2, it was confirmed that when the acidgenerator of the present invention is added, a pattern with smaller LWRcan be formed compared to conventional acid generators shown in theComparative Examples.

Patterning Test by EUV Exposure and Negative-Type Development

The composition for forming a silicon-containing resist underlayer filmSols. 18 to 77 were applied onto a silicon wafer and heated at 240° C.for 60 seconds to prepare silicon-containing films: Film 18 to 77 havinga film thickness of 20 nm.

Subsequently, a resist material having the following componentsdissolved at ratios shown in Table 7 was spin-coated onto the Films 18to 77 and prebaked at 105° C. for 60 seconds using a hot plate toprepare a resist film with a thickness of 60 nm. The resultant wasexposed using an EUV scanner NXE3300 (manufactured by ASML, NA: 0.33, σ:0.9/0.6, quadrupole illumination, with a pitch of 50 nm (on-wafersize)), followed by PEB at 100° C. for 60 seconds on the hot plate. Withrotating at 30 rpm, a developer of butyl acetate was discharged from adeveloper nozzle for 3 seconds, and then the rotation was stopped toperform puddle-development for 27 seconds, spin-drying was performedafter rinsing with diisoamyl ether, and baking was performed at 100° C.for 20 seconds to evaporate the rinse solvent. Thus, hole patterns witha dimension of 25 nm were obtained.

Using a CD-SEM (CG5000) manufactured by Hitachi High-TechnologiesCorporation, an cross-sectional profile at which a hole dimension of 25nm was formed was observed and in this event, the dimensions of 50 holeswere measured, from which the dimensional variation (CDU, 3σ) wasdetermined. The results are shown in Tables 10-1 and 10-2.

TABLE 7 Photo-acid Base resin generator Basic compound SurfactantSolvent (parts by mass) (parts by mass) (parts by mass) (parts by mass)(parts by mass) PR-E1 PRP-E1 (85) PAG-E1 (15.0) Q-E1 (0.3) FC-4430 (0.1)PGMEA(2800) CyHO(1400) PR-E2 PRP-E2 (85) PAG-E1 (15.0) Q-E1 (0.3)FC-4430 (0.1) PGMEA(2800) CyHO(1400)

Surfactant: FC-4430 manufactured by 3M

TABLE 8 Constitutional unit Unit-1 Unit-2 Unit-3 Unit-4 Mw Mw/Mn PRP-E1

9200 1.9 PRP-E2

8500 1.8

TABLE 9 PAG-E1 Q-E1

TABLE 10-1 Silicon- containing resist Sectional underlayer EUV profileof Example film resist hole pattern CDU Example 2-1 Film 18 PR-E1Vertical profile 2.6 Example 2-2 Film 19 PR-E1 Vertical profile 2.8Example 2-3 Film 20 PR-E1 Vertical profile 2.6 Example 2-4 Film 21 PR-E1Vertical profile 2.5 Example 2-5 Film 22 PR-E1 Vertical profile 2.7Example 2-6 Film 23 PR-E1 Vertical profile 2.9 Example 2-7 Film 24 PR-E1Vertical profile 2.8 Example 2-8 Film 25 PR-E1 Vertical profile 2.5Example 2-9 Film 26 PR-E1 Vertical profile 2.5 Example 2-10 Film 27PR-E1 Vertical profile 2.8 Example 2-11 Film 28 PR-E1 Vertical profile2.7 Example 2-12 Film 29 PR-E1 Vertical profile 2.7 Example 2-13 Film 30PR-E1 Vertical profile 2.6 Example 2-14 Film 31 PR-E1 Vertical profile2.7 Example 2-15 Film 32 PR-E1 Vertical profile 2.5 Example 2-16 Film 33PR-E1 Vertical profile 2.7 Example 2-17 Film 34 PR-E1 Vertical profile2.8 Example 2-18 Film 35 PR-E1 Vertical profile 2.6 Example 2-19 Film 36PR-E1 Vertical profile 2.7 Example 2-20 Film 37 PR-E1 Vertical profile2.5 Example 2-21 Film 38 PR-E1 Vertical profile 2.7 Example 2-22 Film 39PR-E1 Vertical profile 2.7 Example 2-23 Film 40 PR-E1 Vertical profile2.8 Example 2-24 Film 41 PR-E1 Vertical profile 2.9 Example 2-25 Film 42PR-E1 Vertical profile 2.8 Example 2-26 Film 43 PR-E2 Vertical profile2.8 Example 2-27 Film 44 PR-E2 Vertical profile 2.6 Example 2-28 Film 45PR-E2 Vertical profile 2.5 Example 2-29 Film 46 PR-E2 Vertical profile2.7 Example 2-30 Film 47 PR-E2 Vertical profile 2.7 Example 2-31 Film 48PR-E2 Vertical profile 2.9 Example 2-32 Film 49 PR-E2 Vertical profile2.6 Example 2-33 Film 50 PR-E2 Vertical profile 2.6 Example 2-34 Film 51PR-E2 Vertical profile 2.6 Example 2-35 Film 52 PR-E2 Vertical profile2.6 Example 2-36 Film 53 PR-E2 Vertical profile 2.6 Example 2-37 Film 54PR-E2 Vertical profile 2.5 Example 2-38 Film 55 PR-E2 Vertical profile2.6 Example 2-39 Film 56 PR-E2 Vertical profile 2.6 Example 2-40 Film 57PR-E2 Vertical profile 2.9 Example 2-41 Film 58 PR-E2 Vertical profile2.8 Example 2-42 Film 59 PR-E2 Vertical profile 2.5

TABLE 10-2 Silicon- containing resist Sectional underlayer EUV profileof Example film resist hole pattern CDU Example 2-43 Film 60 PR-E2Vertical profile 2.7 Example 2-44 Film 61 PR-E2 Vertical profile 2.6Example 2-45 Film 62 PR-E2 Vertical profile 2.6 Example 2-46 Film 63PR-E2 Vertical profile 2.5 Example 2-47 Film 64 PR-E2 Vertical profile2.4 Example 2-48 Film 65 PR-E2 Vertical profile 2.5 Example 2-49 Film 66PR-E2 Vertical profile 2.6 Example 2-50 Film 67 PR-E2 Vertical profile2.6 Example 2-51 Film 68 PR-E2 Vertical profile 2.7 Example 2-52 Film 69PR-E2 Vertical profile 2.4 Example 2-53 Film 70 PR-E2 Vertical profile2.6 Example 2-54 Film 71 PR-E2 Vertical profile 2.6 Example 2-55 Film 72PR-E2 Vertical profile 2.5 Example 2-56 Film 73 PR-E2 Vertical profile2.5 Example 2-57 Film 74 PR-E2 Vertical profile 2.6 Comparative Film 75PR-E1 Vertical profile 3.1 Example 2-1 Comparative Film 76 PR-E1Vertical profile 3.0 Example 2-2 Comparative Film 77 PR-E1 Verticalprofile 3.0 Example 2-3 Comparative Film 75 PR-E2 Vertical profile 3.0Example 2-4 Comparative Film 76 PR-E2 Vertical profile 3.3 Example 2-5Comparative Film 77 PR-E2 Vertical profile 3.1 Example 2-6

As shown in Tables 10-1 and 10-2, it was confirmed that when the acidgenerator of the present invention is added, a pattern excellent in CDUcan be formed compared to conventional acid generators shown in theComparative Examples.

It should be noted that the present invention is not limited to theabove-described embodiments. The embodiments are just examples, and anyexamples that have substantially the same feature and demonstrate thesame functions and effects as those in the technical concept disclosedin claims of the present invention are included in the technical scopeof the present invention.

1. A composition for forming a silicon-containing resist underlayer filmcomprising: a thermosetting silicon-containing material containing anyone or more of a repeating unit shown by the following general formula(Sx−1), a repeating unit shown by the following general formula (Sx−2),and a partial structure shown by the following general formula (Sx−3);and a compound shown by the following general formula (P−0),

wherein R¹ represents an organic group having one or more silanolgroups, hydroxy groups, or carboxy groups, or an organic group fromwhich a protecting group is eliminated by an action of acid and/or heatto generate one or more silanol groups, hydroxy groups, or carboxygroups; R² and R³ are each independently the same as R¹ or eachrepresent a hydrogen atom or a monovalent substituent having 1 to 30carbon atoms, and

wherein in the formula (P−0), R¹⁰⁰ represents a divalent organic groupsubstituted with one or more fluorine atoms, R¹⁰¹ and R¹⁰² eachindependently represents a linear, branched, or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms optionally substitutedwith a hetero atom or optionally interposed by a hetero atom; R¹⁰³represents a linear, branched, or cyclic divalent hydrocarbon grouphaving 1 to 20 carbon atoms optionally substituted with a hetero atom oroptionally interposed by a hetero atom; R¹⁰¹ and R¹⁰², or R¹⁰¹ and R¹⁰³,are optionally bonded to each other to form a ring with a sulfur atom inthe formula; and L¹⁰⁴ represents a single bond or a linear, branched, orcyclic divalent hydrocarbon group having 1 to 20 carbon atoms optionallysubstituted with a hetero atom or optionally interposed by a heteroatom.
 2. The composition for forming a silicon-containing resistunderlayer film according to claim 1, further comprising a crosslinkingcatalyst.
 3. The composition for forming a silicon-containing resistunderlayer film according to claim 2, wherein the crosslinking catalystis a sulfonium salt, an iodonium salt, a phosphonium salt, an ammoniumsalt or a polysiloxane having a structure partially containing one ofthese salts, or an alkaline metal salt.
 4. The composition for forming asilicon-containing resist underlayer film according to claim 1, furthercomprising a nitrogen-containing compound having an acid-decomposablesubstituent.
 5. The composition for forming a silicon-containing resistunderlayer film according to claim 2, further comprising anitrogen-containing compound having an acid-decomposable substituent. 6.The composition for forming a silicon-containing resist underlayer filmaccording to claim 3, further comprising a nitrogen-containing compoundhaving an acid-decomposable substituent.